JP2007093864A - Optical retardation plate, polarizing plate, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical retardation plate incorporated type polarizing plate which contributes to improvement of a display characteristic of a liquid crystal display device and whose productivity is drastically improved; to provide the liquid crystal display device which has an enlarged viewing angle and in which efficiency of using backlight is improved; and to improve adhesion of the optical retardation plate which is effective as a λ/4 plate with optical anisotropic layers multilayered. <P>SOLUTION: The optical retardation plate is manufactured by forming at least two optical anisotropic layers containing at least one kind of liquid crystalline compound on a support, and photo-polymerizing and fixing at least the two optical anisotropic layers sequentially from the substrate side, wherein the rate of polymerization of the layer closest to the support side among the optical anisotropic layers lies in the range of 10 to 90%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a retardation plate, a polarizing plate, and a polarizing plate. In particular, the present invention is used for a reflective liquid crystal display device, a transflective liquid crystal display device, a transmissive liquid crystal display device, a GH-LCD, a PS conversion element, an optical disk writing pickup, a brightness enhancement film, or an antireflection film. The present invention relates to a retardation plate effective as a λ / 4 plate.

  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 a polymer film having an optical axis or slow axis in the oblique direction of the sheet or roll is manufactured. It is very difficult. 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 roll-like film is coated with a coating liquid containing a discotic liquid crystal compound or a rod-like liquid crystal compound, and is oriented in a predetermined direction to develop optical anisotropy. In contrast, 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 a discotic liquid crystalline compound is substantially perpendicular to a film surface (Patent Documents 3, 4, 5, and 6).
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

  In the prior art, problems such as alignment defects and cissing at the time of alignment occurred. Furthermore, it is necessary to modify the polymer in order to impart vertical alignment, or to synthesize the polymer using a special monomer, resulting in an expensive alignment film. A technique for aligning a discotic liquid crystalline compound substantially vertically using an inexpensive alignment film has been demanded. In addition, when a retardation plate is used in a liquid crystal display device, the retardation plate consisting of a layer in which a discotic liquid crystalline compound is substantially vertically aligned has a three-dimensional refractive index so as to be optimal in each liquid crystal mode. It is difficult to develop anisotropy, and a technique that can arbitrarily control the refractive index anisotropy in the three-dimensional direction has been demanded.

  One method for arbitrarily controlling this optical characteristic is to laminate an optically anisotropic layer containing a discotic liquid crystalline compound or a rod-like liquid crystalline compound. In this method, the retardation in the film plane direction is oriented so that the disc surface of the discotic liquid crystal compound is substantially perpendicular to the film surface, or the major axis direction of the rod-like liquid crystal compound is aligned with the film surface. And adjusting the retardation in the direction perpendicular to the film surface by adjusting the thickness of the rod-like liquid crystal compound in the vertical direction so as to obtain an optimum retardation. Thereby, an optimal λ / 4 film can be formed. However, the film including the laminated optically anisotropic layer formed by this method is likely to be peeled off at the boundary of the optically anisotropic layer due to the adhesive on the film surface. There was a problem of getting worse.

  The present invention has been made in view of the above-mentioned problems, and contributes to the improvement of display characteristics of a liquid crystal display device, and provides a retardation plate integrated polarizing plate with significantly improved productivity, and further widens the viewing angle. An object of the present invention is to provide a liquid crystal display device and a liquid crystal display device with improved backlight utilization efficiency. It is another object of the present invention to improve the adhesion of a retardation plate effective as a λ / 4 plate in which an optically anisotropic layer containing a liquid crystalline compound for these purposes is multilayered.

The object of the present invention has been achieved by the following means.
1. At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the retardation plate manufactured by
A retardation film having a polymerization rate of 10 to 90% after photopolymerization of a layer on the support side of the optically anisotropic layer.
2. 2. The retardation plate as described in 1 above, wherein the polymerization rate is 20 to 80%.
3. At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the retardation plate manufactured by
A retardation film having a surface polymerization rate of 1 to 50% after photopolymerization of a layer on the support side of the optically anisotropic layer.
4). The retardation plate as described in any one of 1 to 3 above, wherein each of the at least two optically anisotropic layers contains at least one of a discotic liquid crystalline compound and a rod-like liquid crystalline compound. .
5. The at least two optically anisotropic layers are composed of an optically anisotropic layer containing at least one discotic liquid crystalline compound and an optically anisotropic layer containing at least one rod-like liquid crystalline compound. The retardation film as described in any one of 1 to 4 above.
6). The at least two optically anisotropic layers are composed of an optically anisotropic layer containing a discotic liquid crystalline compound and an optically anisotropic layer containing a rod-like liquid crystalline compound, and the discotic liquid crystal The alignment state is fixed so that the disc surface of the volatile compound is substantially perpendicular to the optically anisotropic layer surface containing the discotic liquid crystalline compound, and the major axis direction of the rod-shaped liquid crystalline compound is 6. The retardation plate according to any one of 1 to 5, wherein the alignment state is fixed so as to be substantially perpendicular to the surface of the optically anisotropic layer containing the rod-like liquid crystalline compound.
7). Each of the at least two optically anisotropic layers is an optically anisotropic layer containing a rod-like liquid crystalline compound, and the major axis direction of the rod-like liquid crystalline compound is substantially in relation to the optically anisotropic layer surface. The position according to any one of 1 to 5 above, wherein the alignment state is fixed so as to be substantially perpendicular to the optically anisotropic layer surface and the layer in which the alignment state is fixed so as to be parallel. Phase difference plate.
8). Any one of 1 to 7 above, wherein the support has an in-plane retardation (Re) of 0 to 20 nm and a thickness direction retardation (Rth) of -100 nm to 100 nm.
The retardation plate described in the item.
9. A polarizing plate comprising the retardation plate according to any one of 1 to 8 and a polarizing film.
10. 9. A liquid crystal display device comprising the retardation plate according to any one of 1 to 8 or the polarizing plate according to 9 and a liquid crystal cell.
11. At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the manufacturing method of the phase difference plate,
A method for producing a retardation film, comprising adjusting the polymerization rate so that the polymerization rate of a layer on the support side of the optically anisotropic layer is 10 to 90%.
12 At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the manufacturing method of the phase difference plate,
A method for producing a retardation plate, comprising adjusting a polymerization rate so that a polymerization rate of a surface of a layer on a support side of the optically anisotropic layer is 1 to 50%.

The retardation plate of the present invention contributes to the improvement of the display characteristics of a liquid crystal display device, can provide a retardation plate integrated polarizing plate with significantly improved productivity, and has a wide viewing angle. And a liquid crystal display device with improved backlight utilization efficiency, which is effective as a λ / 4 plate and has improved adhesion.
In addition, according to the present invention, it is possible to provide a retardation plate integrated polarizing plate with significantly improved productivity, a liquid crystal display device with a wide viewing angle, and a liquid crystal display device with improved backlight utilization efficiency. it can.

Hereinafter, the retardation plate of the present invention will be described in detail.
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. Furthermore, the term “on the support” or “alignment film” as used in the present invention refers to a direct surface of the support or the like and a surface provided with any layer (film) on the support or the like. This is intended to include both cases.

  In this specification, “parallel” and “orthogonal” mean that the angle is within a range of strict angle ± 10 ° or less. 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 °. The “slow axis” means a direction in which the refractive index is maximum in the film plane. 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 is the Re, in-plane slow axis (KOBRA
The retardation value measured by making light of wavelength λ nm incident from the direction inclined + 40 ° with respect to the film normal direction, and the in-plane slow axis as the tilt axis (determined by 21 ADH) as the tilt axis (rotation axis) Retardation values measured in three directions, input values of retardation λ nm from a direction inclined by −40 ° with respect to the normal direction of the film (rotation axis), and assumed values of average refractive index and input KOBRA 21ADH is calculated based on the obtained 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).

[Phase difference plate]
In the present invention, there are two inventions concerning the retardation plate. First, the invention of the first retardation plate (the invention according to claim 1) will be described.
The retardation plate of the present invention is formed by forming at least two optically anisotropic layers containing at least one liquid crystalline compound on a support, and the at least two optically anisotropic layers are formed from the support side. It is produced by sequential photopolymerization and immobilization.
The polymerization rate after photopolymerizing the support-side layer of the optically anisotropic layer is 10 to 90%, preferably 20 to 80%, and more preferably 30 to 80%.
If the polymerization rate is less than 10%, the liquid crystal compound is not sufficiently fixed, resulting in poor alignment and the performance as a λ / 4 plate cannot be obtained. The adhesion with the isotropic layer cannot be improved.

The polymerization rate of the optically anisotropic layer can be examined by measuring an infrared absorption spectrum. Measure the absorbance of a peak near 80 cm ^−1, which is a characteristic absorption band of a polymerization substituent, by infrared spectroscopy after irradiation with ultraviolet rays, which is a preferable light source, for a retardation film including an optically anisotropic layer coated on a transparent support, It can obtain | require as an absorbance ratio of the film before ultraviolet irradiation. This polymerization rate can be adjusted by changing the UV intensity and the irradiation amount when photopolymerizing. The adhesion of the laminated optically anisotropic layer film is deteriorated because the surface side polymerizability after photopolymerization of the optically anisotropic layer on the support side (hereinafter, the layer on the support side may be referred to as “lower layer”). It is considered that the polymerization between the optically anisotropic layer on the side opposite to the support (hereinafter, the layer on the side opposite to the support may be referred to as “upper layer”) does not occur because the number of groups decreases. .

Next, the invention of the second retardation plate will be described.
In the invention of the second retardation plate, at least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are supported. In the retardation plate manufactured by sequentially photopolymerizing from the body side and fixing, the polymerization rate of the surface after photopolymerizing the support side layer of the optically anisotropic layer is compared with the normal polymerization rate 1 to 50%, preferably 3 to 30%. This is to ensure adhesion with the optically anisotropic layer applied to the upper layer.
If the polymerization rate is less than 1%, the liquid crystal compound on the surface is not sufficiently fixed, causing poor alignment, and the performance as a λ / 4 plate cannot be obtained. The adhesion with the optically anisotropic layer to be applied cannot be improved.

The polymerization rate on the surface of the optically anisotropic layer can be examined from an infrared absorption spectrum measured by reflection of a retardation film.
It is known that the photopolymerization reaction is inhibited by oxygen in the air (for example, “Technology Information Association, edited by“ Photocuring Technology—Selection of Resin / Initiator and Compounding Conditions and Degree of Curing / Evaluation ””, p. 114 (2000)). When the polymerization is carried out under conditions in direct contact with oxygen-containing air, the surface is less likely to undergo polymerization. The inventors have further studied and completed the invention because the polymerization rate of the surface is not high as shown in the examples even if the polymerization rate of the optically anisotropic layer is high.
As in the present invention, the polymerization rate of the lowermost optically anisotropic layer and the polymerization rate of the optically anisotropic layer surface can be within the above ranges according to the production method described later.
In the following description of the invention, the same applies to the above-described first retardation plate and second retardation plate unless otherwise specified.

The retardation plate has an in-plane retardation value and a retardation value in the thickness direction as Re and Rth, respectively, and Nz is defined as in the following formula (1), Nz is smaller than 0, specifically Nz Is preferably −5 to −0.1, more preferably −4.5 to −0.2, still more preferably −4 to −0.3, and −4 to −1. Most preferably, it is zero.
Nz = 0.5 + Rth / Re (1)
The retardation value measured from the normal direction of the retardation plate plane is Re (0), and the retardation value measured by tilting the retardation plate by 40 ° is set with the slow axis of the retardation plate as the tilt axis. Re (40), Re (0), Re (40), Re (−40) where Re (−40) is a retardation value measured by tilting the retardation plate by 40 ° in the direction opposite to the tilt direction. ) And the thickness and average refractive index of the retardation plate, the refractive index (Rth) in the thickness direction can be calculated.

  In the retardation plate of the present invention, Re is preferably 50 to 200 nm, more preferably 70 to 180 nm, still more preferably 80 to 160 nm, and most preferably 90 to 160 nm. By being in the above range, it can be suitably used as a λ / 4 plate. Further, it is preferable that the Re (40) and Re (−40) are substantially equal. The difference between Re (40) and Re (−40) is more preferably 0 nm. However, in consideration of measurement error and the like, in this specification, the difference is substantially equal to the range of 4 nm. To do.

The retardation plate of the present invention also preferably has a broadband property in which Re increases as the wavelength increases. For example, there is a technique for laminating a layer having a Re of substantially ½ wavelength and a layer having a Re of substantially ¼ wavelength so that their slow axes intersect each other in order to develop broadband characteristics. It is disclosed in Japanese Unexamined Patent Publication No. 2000-284126. In addition, a technique for developing broadband properties by stretching a modified polycarbonate film is disclosed in International Publication No. 00/26705 pamphlet and the like. Using these techniques, a broadband retardation plate having a desired Re is fabricated, and an optically anisotropic layer containing a liquid crystalline compound is further laminated to control the refractive index in the three-dimensional direction so as to satisfy the above formula (1). be able to.
Rth is preferably −1000 to −20 nm, more preferably −800 to −30 nm, further preferably −600 to −40 nm, and particularly preferably −300 to −100 nm. .

[Optically Anisotropic Layer Containing Liquid Crystalline Compound]
The constituent materials of the optically anisotropic layer used in the retardation plate of the present invention will be described.
In the present invention, two or more optically anisotropic layers are used, but the constituent materials of each layer may be the same or different. The optically anisotropic layer is used as a liquid crystalline compound as an essential component, and if necessary. Those obtained by polymerizing the obtained vertical alignment accelerator with a polymerization initiator can be used. 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.
The liquid crystalline compound used in the present invention is not particularly limited as long as it satisfies the above-mentioned preferable optical characteristics, but a polymerizable liquid crystalline compound is preferably used. By using a polymerizable liquid crystalline compound, an optically anisotropic layer can be formed without using another polymerizable compound. In the present invention, the optically anisotropic layer is a layer formed by fixing the liquid crystalline compound by polymerization or the like, and it is no longer necessary to exhibit liquid crystallinity after becoming a layer. 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.

  The retardation plate of the present invention contains a laminate of two or more optically anisotropic layers. By laminating two or more optically anisotropic layers, it becomes easier to arbitrarily control the refractive index anisotropy in the three-dimensional direction. For example, in the case of a two-layer laminate, a first optical anisotropic layer is formed to set Re to a desired value, and a second optical anisotropic layer is formed to adjust Rth. By doing so, a retardation film satisfying the above formula (1) can be produced. In the present invention, the lower optically anisotropic layer is preferably the above-mentioned first optically anisotropic layer for setting Re to a desired value.

  The liquid crystalline compound used for the first optically anisotropic layer may be a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound. If the retardation plate satisfies the above formula (1), the alignment state of the liquid crystal compound may be any 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 (surface of the optically anisotropic layer) or is in the form of a rod. 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 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 °. . The tilt orientation may be such that the average tilt angle of the disk surface falls within this range, or hybrid orientation in which the tilt angle gradually changes may be used. Even in the case of tilt orientation or hybrid orientation, the average tilt angle is preferably 70 ° to 90 °, more preferably 80 ° to 90 °, and even more preferably 85 ° to 90 °. 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 °. The rod-like liquid crystal compound may be tilted so that the average tilt angle falls within this range, or may be hybrid-aligned so that the tilt angle gradually changes. Even in the case of tilted orientation or hybrid orientation, the average tilt angle is preferably 0 ° to 20 °, more preferably 0 ° to 10 °, and even more preferably 0 ° to 5 °.

  The liquid crystalline compound used in the second optically anisotropic layer may be a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound. If the retardation plate satisfies the above formula (1), the alignment state of the liquid crystal compound may be any of vertical alignment, horizontal alignment, hybrid alignment, and tilt alignment. For controlling the Rth of the phase plate, it is preferable to use a rod-like liquid crystalline compound, and it is more preferred that the major axis of the rod-like liquid crystalline compound is substantially perpendicular to the film surface (optically anisotropic layer surface). That the rod-like liquid crystalline compound is substantially perpendicular 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 70 ° to 90 °. Tilt orientation may be performed so that the average tilt angle falls within this range, or hybrid orientation may be performed so that the tilt angle gradually changes. Even in the case of tilt alignment or hybrid alignment, the average tilt angle of the rod-like liquid crystal compound is preferably 70 ° to 90 °, more preferably 80 ° to 90 °, and still more preferably 85 ° to 90 °.

  The optically anisotropic layer supports a coating liquid containing a liquid crystal compound such as a rod-like liquid crystal compound or a discotic liquid crystal compound and, if desired, the following polymerization initiator, air interface alignment agent, and other additives. It can be formed by applying on the body. It is preferable to form an alignment film on a support and apply the coating solution on the surface of the alignment film.

That is, in the present invention, it is preferable that the at least two optically anisotropic layers each contain at least one of a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound.
The at least two optically anisotropic layers are composed of an optically anisotropic layer containing at least one discotic liquid crystalline compound and an optically anisotropic layer containing at least one rod-like liquid crystalline compound. It can also be set as the structure.
In the present invention, the at least two optically anisotropic layers are composed of an optically anisotropic layer containing a discotic liquid crystalline compound and an optically anisotropic layer containing a rod-like liquid crystalline compound. The rod-like liquid crystal is fixed in an alignment state so that the disc surface of the discotic liquid crystal compound is substantially perpendicular to the optically anisotropic layer surface containing the discotic liquid crystal compound. The alignment state may be fixed so that the long axis direction of the organic compound is substantially perpendicular to the surface of the optically anisotropic layer containing the rod-like liquid crystalline compound.
In the present invention, each of the at least two optically anisotropic layers is an optically anisotropic layer containing a rod-like liquid crystalline compound, and the major axis direction of the rod-like liquid crystalline compound is optically anisotropic. A layer in which the alignment state is fixed so as to be substantially parallel to the layer surface and a structure in which the alignment state is fixed so as to be substantially perpendicular to the surface of the optically anisotropic layer You can also.

[Discotic liquid crystalline compounds]
The discotic liquid crystalline compound used as the liquid crystalline compound in the present invention may be any of 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)) can be used. 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), divalent linking group (L) and 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 crystal compound is preferably 70 to 300 ° C, and more preferably 70 to 170 ° C.

[Bar-shaped liquid crystalline compound]
Examples of the rod-like liquid crystalline compound used as the liquid crystalline compound in the present invention include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano substitution. 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. The rod-like liquid crystalline compound preferably has a polymerizable group so that it can be fixed 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. Nos. 4,683,327, 5,622,648, and 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, and No. 7-110469. 11-80081 and JP-A 2001-328773, and the like can be used.

[Vertical alignment accelerator]
In the present invention, in order to uniformly and vertically align the discotic liquid crystalline compound or the rod-like liquid crystalline compound, the interface side on the support side of the optically anisotropic layer (when the alignment film is provided on the support, “alignment” It is also preferred that the liquid crystal compound be vertically controlled on the side opposite to the support (hereinafter also referred to as “air interface”). For this purpose, it is preferable to use a vertical alignment accelerator.
Examples of the vertical alignment accelerator include a compound that acts to align the liquid crystalline compound vertically by an excluded volume effect, an electrostatic effect or a surface energy effect. And a compound that has a function of vertically aligning a liquid crystalline compound by its excluded volume effect, electrostatic effect, or surface energy effect. That is, the optically anisotropic layer may be formed using a composition (hereinafter, simply referred to as “liquid crystalline composition”) in which the vertical alignment accelerator is preferably blended with the liquid crystalline compound. it can. As such a compound (alignment film interface side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystalline compound on the support side 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. Hereinafter, the vertical alignment accelerator will be described in detail.
The amount of the vertical alignment accelerator used is preferably 0.05 to 4 parts by mass with respect to 100 parts by mass of the liquid crystalline compound, although the preferred range varies depending on the compound used as described later. More preferably, it is 1 part by mass.

[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 an alkyl group or a hydrogen atom having 1 to 5), an alkenylene group, an alkynylene group or an arylene group, and preferably a divalent linking group having 1 to 20 carbon atoms. 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, and is 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 Le group or carbon atoms is preferably an aryl carbonyl group having 7 to 26.
Z may further have a substituent. 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 which may have 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 of -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 liquid crystal composition varies depending on its use, but in the liquid crystal composition (solid content of the liquid crystal composition excluding the solvent when prepared as a coating liquid), 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 “fluorinated polymer”), or a compound represented by the general formula (III) Fluorine compounds are preferably used.

First, the fluorine polymer will be described.
The fluoropolymer usable in the present invention includes a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—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 the 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 or an iodine atom), 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 number of carbon atoms 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 It is particularly preferable that ^b- , an alkylene group or an arylene group is contained. 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 two 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 .

  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, and 1 to 20% by mass of the total amount of the constituent monomers of the fluoropolymer. More preferably, it is 1 to 10% by mass. Since the above-mentioned mass percentage is likely to vary 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. These organic solvents can be used alone or in combination of two or more. 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 used is remarkably influenced by the activity of the chain transfer agent, the combination of the monomers, the polymerization conditions, etc., and needs to 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.

  Preferred content of the fluoropolymer in the liquid crystalline composition for forming the optically anisotropic layer or the like of the present invention (when prepared as a coating liquid, the solid content of the liquid crystalline composition excluding the solvent) The range varies depending on the application, but in the composition (solid content of the composition excluding the solvent in the case of a coating solution), 0.005 to 8% by mass is preferable, and 0.01 to 5% by mass It is more preferable that it is 0.05 to 1% by mass. If the addition amount of the fluorine-based polymer is 0.005% by mass or more, the effect is sufficient, and if it is 8% by mass or less, the coating film is sufficiently dried and performance as an optical film (for example, retardation). The uniformity is not affected, and it is preferable.

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 some 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 preferable range of W is the same as Q in the 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 the 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 the 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 have the same meaning as R ⁰ in the above formula (III), and their preferred ranges are also the same. The carboxyl group (—COOH) represented by W ¹ and W ² 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 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 and 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 or 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. As the carboxyl group, the sulfo group, and the 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, it is an alkylamino group of 1 to 8, more preferably an alkylamino group of 1 to 4. The alkylamino group having a carboxyl group, a sulfo group, or a phosphonoxy group 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 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 its preferred range 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) or a salt thereof represented by W ³ , 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 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. Or an alkylamino group having a salt thereof, 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, pyridyl group, or 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.

  In the specific examples, PTS represents paratoluenesulfonic acid.

The preferred range of the content of the fluorine-containing compound in the liquid crystalline composition varies depending on the use, but 0 in the liquid crystalline composition (solid content of the composition excluding the solvent in the case of a coating liquid). It is preferably 0.005 to 8% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.05 to 1% by mass.
Each of the first optical anisotropic layer and the second optical anisotropy preferably contains the fluorine-containing compound, and more preferably contains one or more kinds of the same fluorine-containing compound. In particular, when the same fluorine-based compound is employed, when the first optical anisotropic layer and the second optical anisotropic layer are laminated, the adhesion between the two layers is improved, which is preferable.

[Horizontal alignment agent]
In the present invention, in order to horizontally align the rod-like liquid crystal compound liquid crystal, it contains at least one compound represented by the following general formulas (IV) to (VI) that contribute to horizontally aligning the molecules of the liquid crystal compound. Is preferred. In the present invention, “horizontal alignment” means that the major axis direction of the liquid crystal compound is parallel to the horizontal plane of the liquid crystal layer, but does not require strictly parallel, In the description, the orientation of the tilt angle formed by the disk plane in the major axis direction of the liquid crystalline compound and the horizontal plane is less than 10 degrees. The inclination angle is preferably 5 degrees or less, more preferably 3 degrees or less, further preferably 2 degrees or less, and most preferably 1 degree or less. The inclination angle may be 0 degree.
Formula (IV)

In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ^{3 each} represent a single bond or a divalent linking group.
General formula (V)

In said formula, R represents a substituent and m represents the integer of 0-5. When m represents an integer greater than or equal to 2, several R may be same or different.
Formula (VI)

In the above formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a substituent.

The compounds represented by formulas (IV) to (VI) will be described in detail below. First, the compound represented by general formula (IV) is demonstrated.
The substituent represented by each of R ¹ , R ² , and R ³ is an alkyl group (preferably an alkyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms). And examples thereof include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group). A group (preferably an alkenyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, such as a vinyl group, an allyl group, a 2-butenyl group, or a 3-pentenyl group. An alkynyl group (preferably an alkynyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 20 carbon atoms). For example, a propargyl group, 3-pentynyl group, etc.), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms). A phenyl group, a p-methylphenyl group, a naphthyl group, etc.), a substituted or unsubstituted amino group (preferably having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, and particularly preferably carbon number). 0 to 20 amino groups such as an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and an anilino group)

An alkoxy group (preferably an alkoxy group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 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 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group. ), An acyl group (preferably an acyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, such as an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group. Etc.), an alkoxycarbonyl group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably carbon number) To 20 alkoxy groups such as a methoxycarbonyl group and an ethoxycarbonyl group), an aryloxycarbonyl group (preferably having 7 to 40 carbon atoms, more preferably having 7 to 30 carbon atoms, and particularly preferably carbon atoms). An aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenyloxycarbonyl group, and an acyloxy group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 carbon atoms). ˜20 acyloxy groups such as an acetoxy group and a benzoyloxy group)

An acylamino group (preferably an acylamino group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, such as an acetylamino group and a benzoylamino group), alkoxycarbonyl An amino group (preferably an alkoxycarbonylamino group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, such as a methoxycarbonylamino group), aryloxy Carbonylamino group (preferably an aryloxycarbonylamino group having 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, particularly preferably 7 to 20 carbon atoms, such as a phenyloxycarbonylamino group) Sulfonylamino group (preferably having 1 to 40 carbon atoms, more preferred Or a sulfonylamino group having 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a methanesulfonylamino group and a benzenesulfonylamino group, and a sulfamoyl group (preferably having a carbon number of 0 to 40). More preferably, it is a sulfamoyl group having 0 to 30 carbon atoms, particularly preferably 0 to 20 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 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as an unsubstituted carbamoyl group, a methylcarbamoyl group, diethylcarbamoyl group Group, phenylcarbamoyl group, etc.),

An alkylthio group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a phenylthio group), a sulfonyl group (preferably having 1 to 1 carbon atoms). 40, more preferably a sulfonyl group having 1 to 30 carbon atoms, particularly preferably a sulfonyl group having 1 to 20 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 40, more Preferably it is C1-C30, Most preferably, it is C1-C20 sulfinyl group, for example, a methane sulfinyl group, a benzene sulfinyl group, etc., a ureido group (preferably C1-C40, more preferable) Is a ureido group having 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as an unsubstituted ureido group or methylurea. And phosphoric acid amide groups (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms), For example, diethyl phosphoric acid amide group, phenylphosphoric acid amide group etc. are mentioned), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group , A nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms such as a nitrogen atom, an oxygen atom, A heterocyclic group having a heteroatom such as a sulfur atom, for example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group Morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, 1,3,5-triazyl group and the like, silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms). Particularly preferred 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 substituents represented by R ¹ , R ² and R ³ are each preferably an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group or a halogen atom.

The divalent linking group represented by X ¹ , X ² and X ³ is an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NR ^a — (R is an alkyl group or a hydrogen atom), 1 to 5 carbon atoms is ^{a - O -, - S -} , - SO -, - is and divalent linking group selected from the group consisting of a combination thereof - SO ₂ It is preferable. The divalent linking group includes at least two divalent linking groups selected from an alkylene group, a phenyl group, —CO—, —NR ^a —, —O—, —S—, —SO ₂ — and a group thereof. More preferred is a combined group.
The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10. An alkylene group, an alkenylene group and a divalent aromatic group are preferably groups exemplified as substituents for the aforementioned R ¹ , R ² and R ³ (for example, alkyl groups, halogen atoms, cyano, alkoxy groups, An acyloxy group).

Among the compounds represented by the general formula (IV), the compounds represented by the following general formula (IVa) or (IVb) are particularly preferable.
Formula (IVa)

In the above formula, R ^1a , R ^2a and R ^3a represent a hydrogen atom or a substituent, X ^1a , X ^2a and X ^3a represent —NH—, —O— or —S—, m1a, m2a and m3a represents an integer of 1 to 3.
Formula (IVb)

In the above formula, Rf ¹ , Rf ² and Rf ³ represent an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, and Y ¹ , Y ² and Y ³ are an alkylene group, —CO—, —NH It represents a group in which at least two divalent linking groups selected from —, —O—, —S—, —SO ₂ — and the group thereof are combined.

First, the compound represented by general formula (IVa) is demonstrated.
The substituent represented by each of R ^1a , R ^2a and R ^3a is R ¹ in the general formula (IV).
, R ² and R ³ , and their preferred ranges are also the same. The substituents represented by R ^1a , R ^2a and R ^3a are particularly preferably alkoxy groups having a CF ₃ group or a CF ₂ H group at the terminal. The alkyl chain contained in the alkoxy group may be linear or branched, preferably has 4 to 20 carbon atoms, more preferably has 4 to 16 carbon atoms, and is particularly preferable. Is 6-16. The alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal is an alkoxy group in which part or all of the hydrogen atoms contained in the alkoxy group are substituted with fluorine atoms. 50% or more of hydrogen atoms in the alkoxy group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted. Examples of alkoxy groups having a CF ₃ group or a CF ₂ H group at the ends represented by R ^1a , R ^2a and R ^3a are shown below.

R1: n-C ₈ F ₁₇ —O—
_{R2: n-C 6 F 13} -O-
_{R3: n-C 4 F 9} -O-
_{R4: n-C 8 F 17} - (CH 2) 2 -O- (CH 2) 2 -O-
_{R5: n-C 6 F 13} - (CH 2) 2 -O- (CH 2) 2 -O-
_{R6: n-C 4 F 9} - (CH 2) 2 -O- (CH 2) 2 -O-
_{R7: n-C 8 F 17} - (CH 2) 3 -O-
_{R8: n-C 6 F 13} - (CH 2) 3 -O-
_{R9: n-C 4 F 9} - (CH 2) 3 -O-
_{R10: H- (CF 2) 8} -O-
R11: H— (CF ₂ ) ₆ —O—
R12: H— (CF ₂ ) ₄ —O—
_{R13: H- (CF 2) 8} - (CH 2) -O-
_{R14: H- (CF 2) 6} - (CH 2) -O-
_{R15: H- (CF 2) 4} - (CH 2) -O-
_{R16: H- (CF 2) 8} - (CH 2) -O- (CH 2) 2 -O-
_{R17: H- (CF 2) 6} - (CH 2) -O- (CH 2) 2 -O-
_{R18: H- (CF 2) 4} - (CH 2) -O- (CH 2) 2 -O-

X ^1a , X ^2a and X ^3a each preferably represent —NH— or —O—, and most preferably represents —NH—. m1a, m2a and m3a are each preferably 2.

Next, the compound represented by general formula (IVb) is demonstrated.
The alkyl group having a CF ₃ group or a CF ₂ H group at the terminal represented by Rf ¹ , Rf ² and Rf ³ may be linear or branched, and preferably has 4 to 4 carbon atoms. It is 20, More preferably, it is C4-C16, Most preferably, it is 6-16. It may have a CF ₃ group or CF ₂ H substituents other than groups. The alkyl group having a CF ₃ group or 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 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. Examples of alkyl groups having a CF ₃ group or a CF ₂ H group at the ends represented by Rf ¹ , Rf ² and Rf ³ are shown below.

Rf1: n-C ₈ F ₁₇ −
_{Rf2: n-C 6 F 13} -
_{Rf3: n-C 4 F 9} -
_{Rf4: n-C 8 F 17} - (CH 2) 2 -
_{Rf5: n-C 6 F 13} - (CH 2) 2 -
_{Rf6: n-C 4 F 9} - (CH 2) 2 -
_{Rf7: H- (CF 2) 8} -
_{Rf8: H- (CF 2) 6} -
_{Rf9: H- (CF 2) 4} -
_{Rf10: H- (CF 2) 8} - (CH 2) -
Rf11: H— (CF ₂ ) ₆ — (CH ₂ ) —
Rf12: H— (CF ₂ ) ₄ — (CH ₂ ) —

Y ¹ , Y ² and Y ³ each preferably represent a group obtained by combining at least two divalent linking groups selected from an alkylene group, —NH—, —O—, —S—, and a group thereof. Particularly preferably an alkylene group, -NH-, -O-, and a group obtained by combining at least two divalent linking groups selected from the group thereof, most preferably -NH-, -O- or —NH (CH ₂ ) _r —O— (r represents an integer of 1 to 8, most preferably 3).

Next, the compound represented by formula (V) will be described.
In the formula (V), the substituent represented by R is synonymous with the substituents represented by R ¹ , R ² , and R ³ in the general formula (IV), and its preferred range is also the same. m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

Among the compounds represented by the general formula (V), a compound represented by the following general formula (Va) is particularly preferable.
General formula (Va)

In the above formula, Rf ^1a , Rf ^2a and Rf ^3a each independently represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, Y ^1a , Y ^2a and Y ^3a are each independently an alkylene group, It represents a group in which at least two divalent linking groups selected from —CO—, —NH—, —O—, —S—, —SO ₂ — and the group thereof are combined.

Examples of the alkyl group having a CF ₃ group or a CF ₂ H group at the ends represented by Rf ^1a , Rf ^2a, and Rf ^3a include those at the ends represented by Rf ¹ , Rf ^2, and Rf ³ in the general formula (IVb). It has the same meaning as alkyl group having a CF ₃ group or CF ₂ H group, and the preferable ranges thereof are also the same. Y ^1a , Y ^2a and Y ^3a are the same as those in formula (IVb). Y ^1, have the same meanings as Y ² and Y ^3, and the preferable ranges thereof are also the same. Most preferably, it is a group obtained by combining at least two divalent linking groups selected from an alkylene group, —O—, and a group thereof.

Finally, the compound represented by formula (VI) will be described.
The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same as the substituents represented by R ¹ , R ² and R ³ in the general formula (IV). The preferred range is also the same.

  Among the compounds represented by the general formula (VI), a compound represented by the following general formula (VIa) is particularly preferable.

In the above formula, Rf ^11a , Rf ^22a , Rf ^33a , Rf ^44a , Rf ^55a and Rf ^66a each independently represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, Y ^11a , Y ^22a , Y ^33a , Y ^44a , Y ^55a and Y ^66a are each independently a divalent group selected from an alkylene group, —CO—, —NH—, —O—, —S—, —SO ₂ — and a group thereof. A group in which at least two connecting groups are combined is represented.

Examples of the alkyl group having a CF ₃ group or a CF ₂ H group at the ends represented by Rf ^11a , Rf ^22a , Rf ^33a , Rf ^44a , Rf ^55a, and Rf ^66a ,
b) has the same meaning as alkyl group having a CF ₃ group or CF ₂ H group at the terminal represented by Rf ^1, Rf ² and Rf ³ in the preferred ranges thereof are also the same. Y ^11a , Y ^22a , Y ³³ _a , Y ^44a , Y ^55a, and Y ^66a are in the general formula (IVb). Y ^1, have the same meanings as Y ² and Y ^3, and the preferable ranges thereof are also the same. Most preferably, it is a group obtained by combining at least two divalent linking groups selected from an alkylene group, —O—, and a group thereof.

  Specific examples of the compound represented by the general formula (IV), (V) or (VI) are shown below, but the compound used in the present invention is not limited thereto. In the following specific examples, no. I-1 to 39 represent general formula (IV), no. I-40 to 50 are general formula (V), No. I-51 to 59 are examples of the compound represented by the general formula (VI).

  The amount of the compound represented by the general formulas (IV) to (VI) is preferably 0.01 to 20% by mass, more preferably 0.03 to 5% by mass with respect to the amount of the liquid crystal compound. 0.05 to 3 mass% is more preferable. In addition, the compound represented by the said general formula (IV)-(VI) may be used independently, and may use 2 or more types together.

[Coating solvent]
As a 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. The coating liquid can be applied by a known method (for example, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

[Polymerization initiator]
The vertically aligned liquid crystal compound is fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a polymerizable group 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 aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970).

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 the polymerization of the liquid crystalline compound 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 polymerizable group-containing liquid crystalline 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 preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the liquid crystalline compound.

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraph Nos. [0028] to [0056] in JP 2001-330725 A, paragraph Nos. [0069] to [0126] in JP 2003-295212 A, and the like. And the compounds described in the above.

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 amount of the polymer added is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the liquid crystalline compound so as not to inhibit the alignment of the liquid crystalline compound. More preferably, it is in the range.
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.

[Support]
The retardation plate of the present invention is formed by forming at least two optically anisotropic layers containing at least one liquid crystalline compound on a support, and the at least two optically anisotropic layers are formed from the support side. Manufactured by sequential photopolymerization and immobilization. Since the support plays a role if the optically anisotropic layer is fixed, it is not always essential in the retardation plate. For example, a phase difference plate having no support can be obtained by forming a two-layer optically anisotropic layer using a metal support as the support and then separating it from the metal support. The retardation plate of the present invention uses a transparent film (transparent support) as a support, and a liquid crystalline composition is applied on the transparent support to form an optically anisotropic layer. A certain phase difference plate is preferable.

As the support, it is preferable to use a polymer film having a small wavelength dispersion. The support preferably further has small optical anisotropy. The support preferably has a light transmittance of 80% or more (transparent support). Specifically, the low chromatic dispersion means that Re (400) /
The ratio of Re (700) is preferably less than 1.2.

  In order to adjust the retardation plate to satisfy the above formula (1), a support having optical anisotropy may be used. The support used in the retardation plate of the present invention preferably has Re of 0 to 20 nm and Rth of −100 nm to 100 nm, Re of 0 to 10 nm, and Rth of −100 nm to 20 nm. preferable.

  Examples of the polymer include cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate and cyclic polyolefin. Among these, a cellulose ester is preferable and a cellulose acetate is more preferable. Cyclic polyolefins include those obtained by hydrogenating a ring-opening polymer of tetracyclododecenes or a ring-opening copolymer of tetracyclododecenes and norbornenes described in JP-B-2-9619. A polymer having a coalescence as a constituent component 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 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, the support is subjected to surface treatment (for example, glow discharge treatment, corona discharge treatment, ultraviolet (UV) Treatment, flame treatment). An adhesive layer (undercoat layer) may be provided on the support. Moreover, in order to give the support body and the long support body the slipperiness in a conveyance process, or to prevent sticking of the back surface and the surface after winding up, the average particle diameter is 10-100 nm inorganic. It is preferable to use a polymer layer in which particles are mixed at a solid content weight ratio of 5% to 40% and formed on one side of the support by coating or co-casting with the support.

  A preferred embodiment of the present invention is an embodiment in which the slow axis of the optically anisotropic layer is not parallel or orthogonal to the longitudinal direction of the support. Specifically, the angle formed by the longitudinal direction of the support and the slow axis of the optically anisotropic layer is preferably 5 to 85 °. 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 Is rubbed in a direction of 5 to 85 ° with respect to the longitudinal direction), making it possible to bond with a long polarizing film at the time of manufacture and roll-to-roll, and the axial angle accuracy of the bonding is high. This makes it possible to manufacture a retardation plate with high productivity.

[Polymer film having optical properties]
The retardation plate of the present invention may contain not only an optically anisotropic layer containing a liquid crystalline compound but also a polymer film in order to control optical properties. The polymer film is formed from a polymer capable of developing birefringence. As the birefringent polymer film, those having excellent controllability of birefringence characteristics, transparency and heat resistance, and those having low photoelasticity are preferable. In this case, the polymer material to be used is not particularly limited as long as it is a polymer that can achieve uniform uniaxial orientation or biaxial orientation, and is preferably a conventionally known material that can be formed by a solution casting method or an extrusion method. , Norbornene polymer, polycarbonate polymer, polyarylate polymer, polyester polymer, aromatic polymer such as polysulfone, polyolefin such as polypropylene, cellulose acylate, or two or three of these polymers Examples thereof include a polymer obtained by mixing the above.

The optical anisotropy of the polymer film is preferably obtained by uniaxial or biaxial stretching. Uniaxial stretching is preferably longitudinal uniaxial stretching using the difference in peripheral speed between two or more rolls, or tenter stretching in which both sides of the polymer film are gripped and stretched in the width direction. Biaxial optical anisotropy may be developed by stretching the polymer film in the longitudinal direction and the transverse direction. In addition, using two or more polymer films, the optical properties of the entire two or more films may satisfy the above conditions. The polymer film is preferably produced by a solvent cast method in order to reduce unevenness in birefringence. The thickness of the polymer film is preferably 20 to 400 nm, and more preferably 30 to 100 nm.

  A polymer film having an optical characteristic in which Rth has a negative value is a method in which a heat-shrinkable film is bonded and heated to apply a predetermined tension while stretching the polymer film in the thickness direction of the film (Japanese Patent Laid-Open No. 2000-2000). 206328, JP 2000-304925) or a method of applying a vinyl carbazole polymer and drying (JP 2001-091746).

[Alignment film]
The retardation plate of the present invention may have an alignment film. That is, an alignment film may be provided on the support, and the liquid crystalline composition may be applied to the surface of the alignment film to align the molecules of the liquid crystal compound. 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 a role, and is not necessarily essential as a component of the present invention. That is, it is possible to produce the retardation 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 support.
The alignment film may be an organic compound (for example, ω-tricosanoic acid) by rubbing treatment of an organic compound (preferably 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 copolymers, styrene copolymers, polyolefins, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide) described in paragraph [0022] of JP-A-8-338913, for example. ), Polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable. .

  70-100% is preferable and, as for the saponification degree of polyvinyl alcohol, 80-100% is more preferable. The polymerization degree of polyvinyl alcohol is preferably 100 to 5000.

In the alignment film of the present invention, a side chain having a crosslinkable functional group (for example, a double bond) is bonded to the main chain, or a crosslinkable functional group having a function of aligning a liquid crystal compound is introduced into the side chain. It is preferable to do. 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 the side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer or the crosslinkable functional group is introduced into the side chain having the function of aligning the liquid crystal compound, 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. Specific examples include those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216.

  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] of JP-A No. 2002-62426. Aldehydes having high reaction activity are preferred, and glutaraldehyde is more 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 generation of reticulation can be obtained.

  The alignment film can be formed by, for example, applying a solution containing the polymer, the crosslinking agent, and the additive, which is an alignment film forming material, onto a transparent support, followed by heat drying (crosslinking) and rubbing treatment. it can. 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 liquid is preferably a mixed solvent of an organic solvent (for example, 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 alignment film and also an optically anisotropic layer reduces significantly.

  As a method for applying the alignment film, 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 is preferable, and a rod coating method is more preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heating and drying can be performed at 20 ° C to 130 ° C. In order to form sufficient crosslinks, 40 ° C to 120 ° C is preferable, and 50 ° C to 110 ° C is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, pH 4.5 to 5.5 is preferable, and 5 is more 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. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

The liquid crystalline composition is applied to the rubbing-treated surface of the alignment film to align the molecules of the liquid crystalline compound. 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.
Moreover, when a 2nd optically anisotropic layer is laminated | stacked on a 1st optically anisotropic layer, the aspect which does not provide an orientation film substantially between the said 2 layers is preferable. The phrase “substantially no alignment film” means that a film formed only for functioning as an alignment film is not included. Even if the surface of the first optically anisotropic layer contributes to the alignment of the liquid crystalline compound of the second optically anisotropic layer, the first optically anisotropic layer is only used as an alignment film. As long as it is not formed for use, it is included in the “substantially no alignment film” regardless of the presence or absence of rubbing.

Next, the manufacturing method of the phase difference plate of this invention is demonstrated.
In the method for producing a retardation plate of the present invention (the method for producing the first retardation plate described above), at least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support. In the method for producing a retardation plate in which the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side, after the support side of the optically anisotropic layer is photopolymerized The polymerization rate is adjusted so that the polymerization rate of the layer is 10 to 90%.
In order to adjust the polymerization rate of the layer on the support side in the optically anisotropic layer within the above range, it can be realized by adjusting the UV irradiation amount. When the UV intensity is 0.5 to 5 kW, the irradiation dose is preferably 50 to 1000 mJ / cm ² .
Further, another manufacturing method of the retardation plate of the present invention (the manufacturing method of the above-described second retardation plate invention) includes at least an optically anisotropic layer containing at least one liquid crystalline compound on a support. In the method for producing a retardation plate, wherein two layers are formed, and the at least two optically anisotropic layers are sequentially photopolymerized from the support side and fixed, among the optically anisotropic layers, the layer on the support side The polymerization rate is adjusted so that the polymerization rate of the surface after photopolymerization of is 1 to 50%.
In order to adjust the polymerization rate of the surface of the layer on the support side of the optically anisotropic layer within the above range, it can be realized by adjusting the UV irradiation amount. When the UV intensity is 0.5 to 5 kW, the irradiation dose is preferably 50 to 1000 mJ / cm ² .

[Polarizer]
Next, the polarizing plate of the present invention will be described.
The polarizing plate of the present invention is formed by laminating the retardation plate of the present invention and a polarizing film. The retardation plate of the present invention can also function as a protective film for a polarizing film. The support preferably functions as a protective film for the polarizing film and is provided as a retardation plate-integrated polarizing plate. Further, the retardation plate of the present invention and a polarizing plate having a protective film may be bonded together.

  Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. 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 by which a polarizing film and a phase difference plate are each laminated | stacked continuously in the elongate state. The long polarizing plate is cut according to the screen size of the liquid crystal display device used.

  If a linearly polarizing film and a retardation plate are combined to form an elliptically polarizing plate, it can be easily incorporated into a reflective and 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 crystalline film produced separately can be further laminated on the long elliptical polarizing plate, it is easy to produce a highly productive brightness enhancement film.

  The polarizing film generally has a protective film. In the present invention, when an optically anisotropic layer made of a liquid crystalline compound is formed on a transparent support, the transparent support can function as a protective film. In the case of using a protective film for the polarizing film separately from the support, it is preferable to use a cellulose ester film or norbornene polymer film having high optical isotropy as the protective film.

[Liquid Crystal Display]
Next, the liquid crystal display device of the present invention will be described.
The liquid crystal display device of the present invention has at least the retardation plate, and includes a reflection type, a semi-transmission type, a transmission type liquid crystal display device and the like. A liquid crystal display device generally includes a polarizing plate, a liquid crystal cell, and a retardation plate, a reflective layer, a light diffusion layer, a backlight, a front light, a light control film, a light guide plate, a prism sheet, a color filter, etc. Although comprised from a member, in this invention, there is no restriction | limiting in particular except the point which makes it essential to use the said phase difference plate. The use position of the retardation plate is not particularly limited, and may be one or more. 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, TN (Twisted Nematic) system, STN (Super Twisted Nematic) system, ECB (Electrically Controlled Birefringence) system, IPS (In-Plane Switching) system, VA (In-Plane Switching) system, VA (In-Plane Switching) system, VA (In-Plane Switching system) Alignment), PVA (Patterned Vertical Alignment), OCB (Optically Compensated Birefringence), HAN (Hybrid Aligned Nematic), ASM (Axially Aligned Asymmetrical)
There are various methods such as a microcell method, a halftone gray scale method, a domain division method, and a display method using a ferroelectric liquid crystal or an antiferroelectric liquid crystal. The driving method of the liquid crystal cell is not particularly limited, and is 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. 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.

  In the liquid crystal display device, the polarizing plate combined with the retardation plate of the present invention functions as an elliptically polarizing plate or a circularly polarizing plate. The liquid crystal display device according to the present invention uses the retardation plate of the present invention at least at one location.

  The retardation plate and polarizing plate of the present invention are not limited to the above uses, and can be used for other various 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]
<Production of cellulose acetate film>
(Preparation of cellulose acetate solution)
Each component shown in 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 having 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 thoroughly mixed for 30 minutes to obtain a silica particle dispersion. This dispersion was put into a disperser together with the components shown in 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)
Each component shown in 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

(Production of cellulose acetate film)
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. In the above composition, the mass ratio of the optical anisotropy reducing agent and the wavelength dispersion adjusting agent to cellulose acetate 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 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 longitudinal direction of the film), and the retardation (Rth) in the thickness direction was −1 nm.

<Preparation of retardation plate 1-1b>
(Formation of alignment film)
After saponifying the surface of the produced cellulose acetate film, 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

(Formation of first optically anisotropic layer)
An optically anisotropic layer coating liquid containing a discotic liquid crystalline compound having the following composition was continuously applied onto the prepared alignment film with a # 3.6 wire bar. 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 60 seconds. Subsequently, the alignment of the liquid crystalline compound is fixed by UV irradiation (UV intensity: 1.8 kW, irradiation amount: 350 mJ / m ² ), and the first optical anisotropic layer which is the optical anisotropic layer on the support side is formed. Then, a retardation plate 1-1a was produced. The polymerization rate at this time is shown in Table 1.

(Composition of the first optically anisotropic layer coating solution)
91 parts by mass of the following discotic liquid crystalline compound Ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9 parts by mass Photopolymerization initiator 3 parts by mass (Irgacure 907, Ciba Specialty) (Chemicals)
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Fluoropolymer P-19 0.4 part by mass Pyridinium salt I-30 0.5 part by mass Methanol 30 parts by mass Methyl ethyl ketone 165 parts by mass

  Discotic liquid crystalline compounds

  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 produced retardation plate 1-1a. Were measured to determine Rth and Nz (Table 3). From these results, the average inclination angle of the disc surface of the discotic liquid crystalline compound with respect to the film surface was 90 °, and it was confirmed that the discotic liquid crystalline compound was aligned perpendicularly 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 °.

(Formation of second optically anisotropic layer)
An optically anisotropic layer coating solution containing a rod-like liquid crystalline compound having the following composition is placed on the alignment film on the first optically anisotropic layer of the prepared retardation plate 1-1a. And continuously applied. In order to dry the solvent of the coating solution and to mature the alignment of the rod-like liquid crystal compound, it was heated with hot air at 90 ° C. for 60 seconds. Subsequently, the orientation of the liquid crystalline compound was fixed by UV irradiation (UV intensity: 1.8 kW, irradiation amount: 350 mJ / m ² ) to form a second optical anisotropic layer. 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 a retardation plate 1-1b.

(Composition of the second optically anisotropic layer coating solution)
The following rod-like liquid crystalline compound A 100 parts by mass Photopolymerization initiator 3 parts by mass (Irgacure 907, manufactured by Ciba Specialty Chemicals)
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Fluoropolymer P-22 0.2 part by mass The following fluoropolymer (D) 0.2 part by mass Pyridinim salt I-12 2 parts by mass Methanol 30 parts by weight Methyl ethyl ketone 168 parts by weight

  Rod-like liquid crystalline compound A

  Fluoropolymer (D)

  In the same manner as described above, Re (0), Re (40), and Re (−40) at 589 nm of the retardation film 1-1b were measured to obtain Rth and Nz. The results are shown in Table 3. From these results, the rod-like liquid crystalline compound is formed on the film surface (optical) on the first optical anisotropic layer in which the discotic liquid crystalline compound is oriented perpendicular to the film surface (optical anisotropic layer surface). It was confirmed that the second optically anisotropic layer oriented perpendicularly to the (anisotropic layer surface) was formed. 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 °.

  In the formation of the first optically anisotropic layer, samples 1-2a to 1-8a having different polymerization rates as shown in Table 1 were prepared by adjusting the UV intensity and the irradiation amount. Re (0), Re (40) and Re (−40) at 589 nm were also measured for the retardation plates 1-2a to 1-8a on which only the first optical anisotropic layer was formed, Rth, and , Nz was obtained and was the same as that of the sample 1-1a. The second optically anisotropic layer was evaluated in the same manner as described above, and adhesion of samples 1-2b to 1-8b was evaluated.

The polymerization rate of the first optically anisotropic layer was measured by measuring the absorbance of a peak near 810 cm ^−1, which is the absorption band of in-plane variable vibration of the acryloyl group, using an infrared absorption spectrophotometer of the prepared retardation film. And obtained from the absorbance ratio of the film before ultraviolet irradiation.

The surface polymerization rate of the first optically anisotropic layer was determined from the absorbance of the peak near 810 cm ⁻¹ by measuring the absorption of the surface reflection of the prepared retardation film using an FT-IR spectrophotometer. .

  For evaluation of adhesion, the prepared retardation film was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. The liquid crystal application surface was cut into 11 vertical and 11 horizontal cuts in a grid pattern with a cutter knife, and the adhesion test on a polyester adhesive tape (No. 31B) manufactured by Nitto Denko Corporation was repeated twice at the same place. It was. The presence or absence of peeling of the hard coat layer was visually observed, and the average value of the results was evaluated in the following four stages.

◎: Out of 100 cases, no peeling was observed ○: Out of 100 cases, peeling was recognized 2 or less △: Out of 100 cases, peeling was recognized 3 10 above or below x: 100 out of 100 are over 10 mm.

[Example 2]
<Preparation of retardation plate 2-1b>
(Formation of first optically anisotropic layer)
The surface of the produced long cellulose acetate film was subjected to saponification treatment, an alignment film was continuously formed in the same manner as in Example 1, and a rubbing treatment was performed in a direction of 45 ° with respect to the longitudinal direction. On the alignment film, a coating solution containing a rod-like liquid crystalline compound having the following composition was continuously applied onto the alignment film with a # 2.0 wire bar. In order to dry the solvent of the coating solution and to mature the alignment of the rod-like liquid crystal compound, it was heated with hot air at 90 ° C. for 60 seconds. Subsequently, the alignment of the liquid crystalline compound is fixed by UV irradiation (UV intensity: 1.8 kW, irradiation amount: 350 mJ / m ² ), and the first optical anisotropic layer which is the optical anisotropic layer on the support side is formed. Then, a retardation film 2-1a was produced. Re (0), Re (40) and Re (−40) at 589 nm are also measured for the retardation film 2-1a on which only the first optical anisotropic layer is formed, and Rth and Nz are obtained. It was. The results are shown in Table 3.

(Composition of the first optically anisotropic layer coating solution)
Rod-like liquid crystalline compound A 100 parts by mass Photopolymerization initiator 3 parts by mass (Irgacure 907, manufactured by Ciba Specialty Chemicals)
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass The following fluoropolymer (F) 0.4 part by mass The above horizontal alignment agent (G) I-13 0.2 part by mass Methyl ethyl ketone 194 parts by mass Part

  Fluoropolymer (F)

  In the same manner as in Example 1, Re (0), Re (40), and Re (−40) at 589 nm of the retardation film 2-1a were measured to obtain Rth and Nz. The results are shown in Table 3. From these results, the average tilt angle of the long axis of the rod-like liquid crystalline compound with respect to the film surface was 0 °, and it was confirmed that the rod-like liquid crystalline compound was aligned horizontally with respect 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 °.

(Formation of second optically anisotropic layer)
An alignment film was formed on the first optical anisotropic layer of the produced retardation plate 2-1a in the same manner as in the case of the first optical anisotropic layer. Subsequently, the second optical anisotropy was changed in the same manner as when the second optical anisotropic layer was formed in Example 1 except that a wire bar of # 3.4 was used on the alignment film. Formed. 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 a retardation plate 2-1b.

  In the same manner as described above, Re (0), Re (40) and Re (-40) at 589 nm of the retardation film 2-1b were measured to obtain Rth and Nz. The results are shown in Table 3. From these results, the rod-like liquid crystalline compound is formed on the film surface (optical anisotropy) on the first optical anisotropic layer in which the rod-like liquid crystal is oriented horizontally with respect to the film surface (optical anisotropic layer surface). It was confirmed that the second optically anisotropic layer oriented perpendicular to the layer surface was formed. 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 °.

  In the formation of the first optical anisotropic layer, samples 2-2a to 2-8a having different polymerization rates as shown in Table 2 were prepared by adjusting the UV intensity and the irradiation amount. Re (0), Re (40) and Re (−40) at 589 nm were also measured for the retardation plates 2-2a to 2-8a on which only the first optical anisotropic layer was formed, Rth, and , Nz was obtained and was the same as that of the sample 1-1a. The second optically anisotropic layer was evaluated in the same manner as described above for the samples 2-2b to 2-8b.

[Example 3]
<Preparation of polarizing plates 1 and 2>
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 the polarizing film has a surface on which the optically anisotropic layer of the produced retardation plate 1-1b is not formed, and the other surface has a viewing angle widening film (WV FILM wide view A WV SA 128). Were bonded together using a polyvinyl alcohol-based adhesive to produce a long polarizing plate 1. The absorption axis of the polarizing film was parallel to the film longitudinal direction, and the slow axis of the wide view film was orthogonal to the film longitudinal direction. The angle formed by the absorption axis of the polarizing film and the slow axis of the retardation plate 1-1b was 45.0 °.
Similarly, the polarizing plate 2 was produced using the phase difference plate 2-1b. In all cases, the absorption axis of the polarizing film was parallel to the film longitudinal direction, and the slow axis of the wide view film was orthogonal to the film longitudinal direction. The angle formed between the absorption axis of the polarizing film and each slow axis of the retardation film 2-1b was 45.0 °.

[Example 4]
<Preparation of polarizing plates 3 and 4>
A long cholesteric liquid crystal film was prepared in the same manner as described in the examples of JP-A-2003-337221. A cholesteric liquid crystal film was continuously pasted on the surface of the polarizing plate 1 on the side opposite to the wide view film to prepare a long polarizing plate 3.
Similarly, the polarizing plate 2 and the cholesteric liquid crystal film were continuously bonded to each other to produce a long polarizing plate 4.

[Comparative example]
<Preparation of polarizing plates 5 and 6>
The retardation plates 1-1a and 2-1a prepared in Examples 1 and 2 were subjected to continuous saponification treatment on the surface of the cellulose acetate film opposite to the surface on which the optically anisotropic layer was formed. In the same manner as in Example 3, a long polarizing film was prepared, and the optically anisotropic layers of the prepared retardation plates 1-1a and 2-1a were formed on one surface of the polarizing film. A long-view polarizing plate 5 and 6 was prepared by continuously laminating a wide view film on the other surface and a non-surface. The absorption axis of the polarizing film was parallel to the film longitudinal direction, and the slow axis of the wide view film was orthogonal to the film longitudinal direction. The angle formed between the absorption axis of the polarizing film and the slow axis of the phase difference plates 1-1a and 2-1a was 45.0 °.

<Preparation of polarizing plates 7 and 8>
In the same manner as in Example 4, a long cholesteric liquid crystal film was prepared, and the surfaces of the polarizing plates 5 and 6 opposite to the wide-view film and the cholesteric liquid crystal film were continuously bonded to each other to obtain a long Polarizing plates 7 and 8 were produced.

[Example 5]
<Production of liquid crystal display device>
Of the pair of polarizing plates provided in the liquid crystal display device (AQUAS LC20C1S, manufactured by Sharp Corporation) using a TN type liquid crystal cell, only the polarizing plate on the backlight side is peeled off, and the above-prepared polarizing plate 3 is used instead. 4, 7 and 8 were attached via an adhesive such that the wide view film was on the liquid crystal cell side. The transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side were arranged to be in the O mode.
About the produced liquid crystal display device, the viewing angle was measured from black display (L1) to white display (L8) using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM). The front luminance during white display with respect to the case where the polarizing plate 8 is used is 1.00, and is shown as a relative value in Table 4. Further, when the white display was observed from an oblique direction, the coloring was small when the polarizing plates 3 and 4 were used, compared to the case where the polarizing plates 7 and 8 were used.

Claims (12)

At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the retardation plate manufactured by
A retardation film having a polymerization rate of 10 to 90% after photopolymerization of a layer on the support side of the optically anisotropic layer.   The retardation plate according to claim 1, wherein the polymerization rate is 20 to 80%. At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the retardation plate manufactured by
A retardation film having a surface polymerization rate of 1 to 50% after photopolymerization of a layer on the support side of the optically anisotropic layer.   The retardation according to any one of claims 1 to 3, wherein each of the at least two optically anisotropic layers contains at least one of a discotic liquid crystalline compound and a rod-shaped liquid crystalline compound. Board.   The at least two optically anisotropic layers are composed of an optically anisotropic layer containing at least one discotic liquid crystalline compound and an optically anisotropic layer containing at least one rod-like liquid crystalline compound. The retardation film according to claim 1, wherein the retardation film is a retardation film.   The at least two optically anisotropic layers are composed of an optically anisotropic layer containing a discotic liquid crystalline compound and an optically anisotropic layer containing a rod-like liquid crystalline compound, and the discotic liquid crystal The alignment state is fixed so that the disc surface of the volatile compound is substantially perpendicular to the optically anisotropic layer surface containing the discotic liquid crystalline compound, and the major axis direction of the rod-shaped liquid crystalline compound is The phase difference plate according to claim 1, wherein the alignment state is fixed so as to be substantially perpendicular to the surface of the optically anisotropic layer containing the rod-like liquid crystalline compound.   Each of the at least two optically anisotropic layers is an optically anisotropic layer containing a rod-like liquid crystalline compound, and the major axis direction of the rod-like liquid crystalline compound is substantially in relation to the optically anisotropic layer surface. The alignment state is fixed so as to be substantially perpendicular to the optically anisotropic layer surface and the layer in which the alignment state is fixed so as to be parallel to each other. Phase difference plate.   The retardation according to any one of claims 1 to 7, wherein the support has an in-plane retardation (Re) of 0 to 20 nm and a thickness direction retardation (Rth) of -100 nm to 100 nm. Board.   A polarizing plate comprising the retardation plate according to claim 1 and a polarizing film.   A liquid crystal display device comprising the retardation plate according to claim 1 or the polarizing plate according to claim 9 and a liquid crystal cell. At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the manufacturing method of the phase difference plate,
A method for producing a retardation film, comprising adjusting the polymerization rate so that the polymerization rate of a layer on the support side of the optically anisotropic layer is 10 to 90%. At least two optically anisotropic layers containing at least one liquid crystalline compound are formed on a support, and the at least two optically anisotropic layers are sequentially photopolymerized and fixed from the support side. In the manufacturing method of the phase difference plate,
A method for producing a retardation plate, comprising adjusting a polymerization rate so that a polymerization rate of a surface of a layer on a support side of the optically anisotropic layer is 1 to 50%.