JP2007193276A - Optical compensation film, polarizing plate and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical compensation film which fully demonstrates optical compensation ability without spoiling frontal contrast of a liquid crystal display apparatus. <P>SOLUTION: The optical compensation film contains at least a 1st optical anisotropic layer and a 2nd optical anisotropic layer. In-plane retardation of the 1st optical anisotropic layer is 0 to 10 nm and retardation in a thickness direction is -400 to -80 nm. In-plane retardation of the 2nd optical anisotropic layer is 20 to 150 nm and retardation in the thickness direction is 100 to 300 nm. The optical compensation film satisfies a relational formula (1): 0<Hz(B+L)<1.0%, a relational formula (2): 0<Hz(B)<1.0% and a relational formula (3): Hz(B+L)/Hz(B)<1.3, wherein Hz(B)(%) denotes haze of the 2nd optical anisotropic layer and Hz(B+L)(%) denotes haze of a laminated body constituted of the 1st optical anisotropic layer and the 2nd optical anisotropic layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to the technical field of liquid crystal display devices, and more particularly, to IPS mode and FFS mode liquid crystal display devices and the like. The present invention also relates to an optical compensation film that contributes to improvement in display characteristics of a liquid crystal display device such as an IPS mode, in particular, an increase in viewing angle, and a polarizing plate using the same.

  As a liquid crystal display device, a so-called TN mode, in which a liquid crystal layer in which nematic liquid crystal is twisted and arranged between two orthogonal polarizing plates, and an electric field is applied in a direction perpendicular to the substrate is widely used. In this method, since the liquid crystal rises with respect to the substrate during black display, birefringence due to the liquid crystalline compound occurs when viewed from an oblique direction, and light leakage occurs. In order to solve this problem, a system in which a liquid crystal cell is optically compensated and a light leakage is prevented by using a film in which liquid crystal compounds are hybrid-aligned has been put into practical use. However, even if a liquid crystal compound is used, it is very difficult to completely optically compensate the liquid crystal cell without any problem, resulting in a problem that gradation reversal in the lower direction of the screen cannot be suppressed.

  In order to solve such a problem, a liquid crystal display device using a so-called IPS mode or FFS mode in which a lateral electric field is applied to the liquid crystal, a protrusion formed in the panel by vertically aligning a liquid crystal having a negative dielectric anisotropy, A vertical alignment (VA) mode in which alignment is divided by a slit electrode has been proposed and put into practical use. In recent years, these panels have been developed not only for monitor applications but also for TV applications, and screen brightness has been greatly improved accordingly. For this reason, slight light leakage in the diagonally oblique incidence direction during black display, which has not been considered as a problem in these operation modes, has become apparent as a cause of deterioration in display quality.

  As one means for improving the color tone and the viewing angle of black display, disposing an optical compensation material having birefringence characteristics between the liquid crystal layer and the polarizing plate is also studied in the IPS and FFS modes. For example, by arranging a birefringent medium having an optical axis orthogonal to each other to compensate for increase / decrease in retardation of the liquid crystal layer at the time of inclination between the substrate and the polarizing plate, white display or halftone display can be performed from an oblique direction. It has been disclosed that coloring in direct viewing can be improved (see Patent Document 1). In addition, as a method using an optical compensation film made of a styrene polymer having a negative intrinsic birefringence or a discotic liquid crystalline compound (see Patent Documents 2, 3, and 4), the optical compensation film has a positive birefringence and an optical axis. A method of combining a film in the plane of a film with a film having a positive birefringence and an optical axis in the normal direction of the film (see Patent Document 5), a biaxial optical compensation sheet having a retardation of half a wavelength A method of using (see Patent Document 6) and a method of using a film having a negative retardation as a protective film of a polarizing plate and providing an optical compensation layer having a positive retardation on this surface (see Patent Document 7) have been proposed. .

Japanese Patent Laid-Open No. 9-80424 Japanese Patent Laid-Open No. 10-54982 JP-A-11-202323 Japanese Patent Laid-Open No. 9-292522 JP 11-133408 A JP-A-11-305217 JP-A-10-307291

  The present invention has been made in view of the above-mentioned problems, and it does not reduce front contrast of a liquid crystal display device, particularly a liquid crystal display device in an IPS mode or an FFS mode, and leaks light from an oblique direction, for example, 60 °. It is an object of the present invention to provide an optical compensation film and a polarizing plate that contribute to the reduction of color change. Another object of the present invention is to provide a liquid crystal display device with low black luminance and an improved front contrast ratio, particularly an IPS mode liquid crystal display device.

Means for solving the above-mentioned problems are as follows.
[1] It includes at least a first optical anisotropic layer and a second optical anisotropic layer, the in-plane retardation of the first optical anisotropic layer is 0 to 10 nm, and the retardation in the thickness direction Is an optical compensation film having an in-plane retardation of the second optically anisotropic layer of 20 to 150 nm and a retardation in the thickness direction of 100 to 300 nm, The haze of the optically anisotropic layer 2 is set to Hz (B) (%), and the haze made of the laminate of the first optically anisotropic layer and the second optically anisotropic layer is set to Hz (B + L). (%), An optical compensation film satisfying the following relational expressions (1) to (3):
(1) 0 <Hz (B + L) <1.0%
(2) 0 <Hz (B) <1.0%
(3) Hz (B + L) / Hz (B) <1.3.

[2] The optical compensation film according to [1], wherein the second optically anisotropic layer is made of a cellulose acylate film stretched by a transverse stretching method, a longitudinal stretching method, a simultaneous biaxial stretching method, or a sequential biaxial stretching method. .
[3] The first optically anisotropic layer is composed of a composition containing a rod-like liquid crystal compound, and the molecules of the rod-like liquid crystal compound are aligned substantially perpendicular to the layer surface in the layer, The optical compensation film of [1] or [2] fixed in an orientation state.
[4] A copolymer (polymer A) in which the first optically anisotropic layer contains a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1) The optical compensation film according to any one of [1] to [3], which contains at least one kind:

General formula (1)

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent; L is selected from a divalent linking group selected from the following linking group group or the following linking group group. Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q is 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, or a hydrophilic group (—OH). Represents.

[5] The optical compensation film according to any one of [1] to [4], wherein the first optically anisotropic layer contains at least one onium salt.
[6] A polarizing plate having the optical compensation film of any one of [1] to [5] and a polarizing film.
[7] The polarizing plate according to [6], wherein only a substantially isotropic adhesive layer and / or a substantially isotropic protective film is included between the optical compensation film and the polarizing film.
[8] The polarizing plate according to [7], wherein the transparent protective film is a film containing cellulose acylate, the in-plane retardation is 0 to 10 nm, and the retardation in the thickness direction is -20 to 20 nm.
[9] The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and the slow phase of the second optical anisotropic layer The polarizing plate according to any one of [6] to [8], wherein the direction of the axis and the direction of the absorption axis of the polarizing film are substantially perpendicular to each other.
[10] The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are stacked in this order, and the second optical anisotropic layer is delayed. The polarizing plate according to any one of [6] to [8], wherein the direction of the phase axis and the direction of the absorption axis of the polarizing film are substantially parallel.
[11] A liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate of [9] The first optically anisotropic layer, the second optically anisotropic layer, and the polarizing film are arranged in this order on the outside of one of the pair of substrates, and the second optically anisotropic layer The polarizing plate is disposed so that the slow axis and the major axis direction of the liquid crystal molecules during black display are substantially parallel, and a second polarizing film is further provided outside the other substrate. Liquid crystal display device in which the absorption axes of the polarizing films are orthogonal to each other.
[12] A liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate when displaying black, and a polarizing plate according to [10] The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are arranged in this order on the outer side of one of the pair of substrates, and the second optical anisotropic layer is delayed. The polarizing plate is disposed so that the phase axis and the major axis direction of the liquid crystal molecules at the time of black display are substantially orthogonal to each other, and a second polarizing film is further provided on the outside of the other substrate. A liquid crystal display device in which the absorption axes of the films are orthogonal to each other.
[13] Only a substantially isotropic adhesive layer and / or a substantially isotropic transparent protective film is included between the second polarizing film and the substrate [11] or [ 12] The liquid crystal display device.
[14] The transparent protective film is a film containing cellulose acylate, the in-plane retardation is 0 to 10 nm, the retardation in the thickness direction is -20 to 20 nm, and the haze of the transparent protective film is 1. [13] The liquid crystal display device of 0% or less.

  The optical compensation film of the present invention has predetermined optical characteristics, and haze satisfies a predetermined relational expression. By using the optical compensation film of the present invention and the polarizing plate of the present invention using the optical compensation film, a high-quality liquid crystal display device having high front contrast can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

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

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

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

  In the present specification, Re and Rth respectively represent in-plane retardation and retardation in the thickness direction at a certain wavelength λ nm. Re is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) by making light of wavelength λ nm incident in the normal direction of the film. Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the film with the slow axis in the plane (determined by KOBRA 21ADH) as the tilt axis (rotation axis). The retardation value and the retardation value measured by making light of wavelength λ nm incident from a direction inclined −40 ° with respect to the normal direction of the film with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value. Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness.

[Optical compensation film]
The optical compensation film of the present invention has first and second optical anisotropic layers each having predetermined optical characteristics, the single haze value of the second optical anisotropic layer, and the second and first The haze value of the laminated body of optically anisotropic layers satisfies a predetermined relationship.

[Haze]
The second optically anisotropic layer haze value (Hz (B)) of the optical compensation film of the present invention is less than 1.0%. More preferably, it is 0.8% or less. Further, the haze (Hz (B + L)) of the laminate of the second optical anisotropic layer and the first optical anisotropic layer is less than 1.0%, that is, the second optical anisotropy. Even if the layer and the first optically anisotropic layer are laminated, the haze is less than 1.0%. The Hz (B + L) is more preferably 0.8% or less. Further, the haze of the laminate of the first and second optically anisotropic layers and the haze of the second optically anisotropic layer should satisfy Hz (B + L) / Hz (B) <1.3. Preferably, it is more preferable to satisfy Hz (B + L) / Hz (B) <1.0. When the optical compensation film of the present invention having such characteristics is used, viewing angle characteristics can be improved with almost no reduction in front contrast when incorporated in a liquid crystal display device.
The haze of the optically anisotropic layer and the optical compensation film can be measured using various haze meters, for example, a haze meter (NDH2000) manufactured by Nippon Denshoku Industries Co., Ltd.

  The haze value of a polymer film can be lowered by generally suppressing the amount of additive added to the film. Therefore, when the second optically anisotropic layer is formed from a polymer film to be described later, the addition amount of the retardation increasing agent is controlled so that the haze value (Hz (B)) is less than 0.1. Is preferred. Moreover, usually, even if the haze values of both optically anisotropic layers are small, the haze value may increase when laminated. In the present invention, the haze value of the laminate in which the first and second optically anisotropic layers are laminated is also small, specifically less than 1.0%. Thus, in order to keep the haze value small as a laminate, a polymer film (preferably a cellulose acylate film) is used as the second optically anisotropic layer, and the vertical orientation ( It is preferable to use a film containing rod-like liquid crystal molecules having homeotropic alignment. It was found that laminating a film containing homeotropically aligned liquid crystal molecules on a polymer film contributes to reducing the haze below the haze of the laminate.

Hereinafter, materials, methods, various characteristics and the like used for the production of the optical compensation film of the present invention will be described in detail.
First, the second optical anisotropic layer will be described.
[Second optically anisotropic layer]
The in-plane retardation Re of the second optically anisotropic layer is preferably 20 to 150 nm, more preferably 30 to 130 nm, and still more preferably 40 to 110 nm. Furthermore, the retardation Rth in the thickness direction is preferably 100 to 300 nm, more preferably 120 to 280 nm, and still more preferably 140 nm to 260 nm. The second optically anisotropic layer is not particularly limited as long as it is a compound capable of obtaining the above optical characteristics, but in the present invention, it is preferable to use a cellulose acylate film.

[Cellulose acylate film]
The cellulose acylate film is a film containing a cellulose acylate compound and a compound having an ester-substituted cellulose skeleton obtained by introducing a functional group biologically or chemically using cellulose as a raw material. Cellulose acylate is an ester of cellulose and acid. The acid constituting the ester is preferably an organic acid, more preferably a carboxylic acid, still more preferably a fatty acid having 2 to 22 carbon atoms, still more preferably a lower fatty acid having 2 to 4 carbon atoms, and most preferably acetic acid. .

Cellulose acylate is an ester of cellulose and carboxylic acid. In cellulose acylate, all or part of the hydrogen atoms of the hydroxyl groups present at the 2-position, 3-position and 6-position of the glucose unit constituting cellulose are substituted with acyl groups. Examples of acyl groups include acetyl, propionyl, butanoyl, isobutanoyl, tert-butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl Group, octadecanoyl group, cyclohexanecarbonyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group. Acetyl group, propionyl group, butanoyl group, dodecanoyl group, octadecanoyl group, tert-butanoyl group, oleoyl group, benzoyl group, naphthylcarbonyl group and cinnamoyl group are preferable, acetyl group, propionyl group and butanoyl group are more preferable. An acetyl group is most preferred.
The cellulose acylate may be an ester of cellulose and a plurality of acids. The cellulose acylate may be substituted with a plurality of acyl groups.

  The degree of polymerization of the cellulose acylate is preferably from 200 to 700, more preferably from 250 to 550, even more preferably from 250 to 400, and most preferably from 250 to 350 in terms of viscosity average degree of polymerization. The viscosity average degree of polymerization can be measured according to Uda et al.'S limiting viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Science, Vol. 18, No. 1, pages 105-120, 1962). A method for measuring the viscosity average degree of polymerization is also described in JP-A-9-95538.

Cellulose acylate with a small amount of low molecular components has a high average molecular weight (degree of polymerization), but its viscosity is lower than that of ordinary cellulose acylate. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular components can be performed by washing the cellulose acylate with an appropriate organic solvent. In addition, cellulose acylate having a small amount of low molecular components can be synthesized. When manufacturing a cellulose acylate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass of cellulose. When the amount of the sulfuric acid catalyst is within the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized.
The cellulose acylate raw material cotton and the synthesis method are also described in pages 7 to 12 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Invention).

  In the cellulose acylate film, the polymer component constituting the film is preferably substantially composed of cellulose acylate. “Substantially” means 55% by mass or more (preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more) of the polymer component. Two or more types of cellulose acylate may be used in combination with the cellulose acylate film.

  The cellulose acylate used for producing the cellulose acylate film is obtained using cellulose as a raw material. Examples of cellulose include cotton linter and wood pulp (hardwood pulp, conifer pulp). Cellulose acylate obtained from any raw material cellulose can be used, and in some cases, a mixture may be used. Detailed descriptions of these raw material celluloses include, for example, the plastic material course (17) Fibrous resin (manufactured by Marusawa and Uda, Nikkan Kogyo Shimbun, published in 1970), and the Japan Institute of Technical Disclosure (public technical number 2001-). 1745, issued on Mar. 15, 2001, Invention Association), pages 7 to 8 can be used, and the cellulose acylate film is not particularly limited.

  The cellulose acylate film is preferably a film obtained by preparing a solution of cellulose acylate and forming the solution using a solvent casting method. Details of the method for producing a cellulose acylate film using the solvent cast method are described in JP-A-2005-331773, [0095] to [0096], and can also be used in the present invention. In the cellulose acylate solution, as additives, for example, a plasticizer, an ultraviolet absorber, a deterioration preventing agent, an Re developing agent, an Rth reducing agent, a wavelength dispersion adjusting agent, fine particles, a peeling accelerator, an infrared absorber, and the like. Can be added. In the present invention, it is preferable to use a retardation adjusting agent (Re adjusting agent). Moreover, it is preferable to use 1 or more types of a plasticizer, a ultraviolet absorber, and a peeling accelerator.

[Re adjuster]
In order to produce a cellulose acylate film that satisfies the optical properties required for the second optically anisotropic layer, it is preferable to use a Re adjuster. Here, the term “Re adjuster” is used for any agent that increases, decreases or develops the retardation Re. Examples of the Re adjusting agent that can be used in the present invention include those made of a rod-like or discotic compound. As the rod-like or discotic compound, a compound having at least two aromatic rings can be used. The addition amount of the Re developing agent composed of the rod-shaped compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate. preferable.

  The disc-shaped Re adjuster is preferably used in a range of 0.05 to 20 parts by mass, and in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer component containing the cellulose acylate. More preferably, it is more preferably used in the range of 0.2 to 5 parts by mass, and most preferably in the range of 0.5 to 2 parts by mass. Two or more types of Re developing agents may be used in combination. The Re enhancer comprising a rod-like or discotic compound preferably has a maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region. Specifically, a compound having a rod shape is shown below.

  In order to satisfy the optical properties required for the second optically anisotropic layer, the cellulose acylate film obtained by a solvent cast method or the like may be further subjected to a stretching treatment. The stretching treatment may be any of a lateral stretching method, a longitudinal stretching method, a simultaneous biaxial stretching method, and a sequential biaxial stretching method. Regarding stretching of the cellulose acylate film, see JP-A-62-115035, JP-A-4-152125, JP-A-4-284221, JP-A-4-298310, and JP-A-11-48271. Details are described and can be used in the present invention.

[First optically anisotropic layer]
The in-plane retardation Re of the first optical anisotropic layer contained in the optical compensation film of the present invention is preferably 0 to 10 nm, more preferably 0 to 5 nm, and 0 to 3 nm. Is more preferable. Further, the retardation Rth in the thickness direction of the optically anisotropic layer is preferably −400 to −80 nm, more preferably −360 to −100 nm, and further preferably −320 to −120 nm. preferable.

  The first optically anisotropic layer is preferably formed from a composition containing a liquid crystal compound. The liquid crystal compound is preferably a rod-like liquid crystal compound. When a rod-like liquid crystal compound is used, it is preferable that rod-like molecules are aligned perpendicular to the layer plane in the optically anisotropic layer.

  The type of liquid crystal compound is not particularly limited. The first optically anisotropic layer included in the optical compensation film of the present invention may be prepared, for example, by forming a low molecular liquid crystal compound in a nematic orientation in a liquid crystal state and then immobilizing it by photocrosslinking or thermal crosslinking. . Alternatively, the polymer liquid crystalline compound may be formed in a nematic alignment in a liquid crystal state and then cooled to cool the alignment. In the present invention, a liquid crystalline compound is used for the production of the optically anisotropic layer, but the liquid crystalline compound is often contained in the optically anisotropic layer in a state of being fixed by polymerization or the like in the production process. Finally, it is not necessary to show liquid crystallinity. The polymerizable liquid crystal compound may be a polyfunctional polymerizable liquid crystal or a monofunctional polymerizable liquid crystal compound.

  In the first optically anisotropic layer included in the optical compensation film of the present invention, the molecules of the liquid crystal compound are preferably fixed in a predetermined alignment state, preferably in a vertical alignment state. The term “substantially perpendicular to the rod-like liquid crystalline compound” means that the angle formed by the layer plane and the director of the rod-like liquid crystalline compound is in the range of 70 ° to 90 °. 80 ° to 90 ° are more preferable, and 85 ° to 90 ° are more preferable.

Hereinafter, materials used for production, production methods, and the like will be described in detail with respect to an aspect of an optical compensation film having an optical anisotropic layer containing a liquid crystalline compound as the first optical anisotropic layer.
The optically anisotropic layer can be formed from a composition containing a liquid crystalline compound such as a rod-like liquid crystalline compound and, if desired, the following polymerization initiator, alignment controller and other additives.

[Bar-shaped liquid crystalline compound]
In the present invention, it is preferable to form the first optically anisotropic layer using a rod-like liquid crystalline compound. Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. It is more preferable to fix the alignment of the rod-like liquid crystal compound by polymerization. As the liquid crystalline compound, those having a partial structure capable of causing polymerization or crosslinking reaction by actinic rays, electron beams, heat, or the like are suitably used. The number of the partial structures is preferably 1 to 6, more preferably 1 to 3. As the polymerizable rod-like liquid crystalline compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 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, JP 2001-328773, JP 2004-240188, JP 2005-99236, JP 2005-99237, JP 2005-121827, JP It is possible to use the compounds described in 2002-30042 That.

[Copolymer of fluoroaliphatic-containing monomer and general formula (1)]
The first optically anisotropic layer preferably contains a fluoroaliphatic-containing polymer containing a repeating unit represented by the following general formula (1) (hereinafter sometimes referred to as “polymer A”). . The polymer A mainly contributes to vertically aligning the molecules of the liquid crystalline compound at the air interface of the optically anisotropic layer.

General formula (1)

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent. Q is 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 a hydrophilic group (—OH). Represents. 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 ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent selected from the following substituent group exemplified in JP-A-2004-333852.
(Substituent group)
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly 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, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferred). Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. Aralkyl groups (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as benzyl group, phenethyl group, 3- Phenylpropyl group and the like), a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, Unsubstituted amino group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly 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, particularly 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, particularly 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, particularly preferably 2-10 carbon atoms. A silamino group, for example, an acetylamino group, a benzoylamino group, and the like, an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 12 carbon atoms). An alkoxycarbonylamino group, for example, a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms). Aryloxycarbonylamino group, for example, phenyloxycarbonylamino group and the like, sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12 sulfonylamino groups such as methanesulfonyl And sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl group). 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, and particularly preferably carbon number). 1 to 12 carbamoyl groups, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group and the like),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is 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, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted 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, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a 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, particularly preferably 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 ³ are each independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), 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. More preferably, it is particularly preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, most preferably R ² and R ³ are a hydrogen atom, and R ¹ is a hydrogen atom or a methyl group. 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 ^{4 in} —NR ⁴ — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom or an alkyl group. R ⁵ in —PO (OR ⁵ ) — represents an alkyl group, an aryl group or an aralkyl group, and preferably an alkyl group. The carbon number when R ⁴ and R ⁵ represent an alkyl group, an aryl group or an aralkyl group is the same as that described in the “substituent group”. L preferably contains a single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, an alkylene group or an arylene group, and is a single bond, —CO—, —O—. , —NR ⁴ —, an alkylene group or an arylene group is particularly preferable, and a single bond is most preferable. When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of particularly preferred alkylene groups include methylene, ethylene, trimethylene, tetrabutylene, hexamethylene groups and the like. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene 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 particularly 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 those similar to the substituents exemplified above as the substituents for R ^{1 to} R ³ .
Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

  In the formula (1), 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, trimethyl). Benzylammonium, dimethylphenylammonium, etc.), pyridinium salts, etc.), sulfo groups, salts of sulfo groups (examples of cations forming salts are the same as those described above for carboxyl groups), phosphonoxy groups, salts of phosphonoxy groups (salts) Examples of the cation that forms are the same as those described above for the carboxyl group) and a hydrophilic group (hydroxyl group). A carboxyl group, a sulfo group, a phospho group, and a hydrophilic group are more preferable, and a carboxyl group or a hydrophilic group is particularly preferable.

  Although the specific example of the monomer corresponding to the said General formula (1) contained in the said polymer A which can be used for this invention is given below, this invention is not restrict | limited at all by the following specific examples.

  The polymer A may contain one type of repeating unit represented by the general formula (1), or may contain two or more types. The polymer A may have one or more repeating units derived from the fluoroaliphatic group-containing monomer. Preferably, it contains a fluoroaliphatic group-containing monomer described in general formula [1] of JP-A No. 2004-333852. Furthermore, the polymer A may contain other repeating units. The other repeating units are not particularly limited, and preferred examples thereof include repeating units derived from ordinary radical polymerizable monomers. The polymer A may contain one type of repeating unit derived from a monomer selected from the monomer group described in JP-A-2004-46038 [0026] to [0033], or may contain two or more types. Good.

  The polymer A may contain a repeating unit derived from a monomer represented by the general formula [2] described in JP-A-2004-333852.

  The amount of the fluoroaliphatic group-containing monomer of the polymer A 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. Further preferred. In the repeating unit derived from the fluoroaliphatic group-containing monomer, the amount of the repeating unit represented by the general formula (1) is 0 of the total amount of constituent monomers of the repeating unit derived from the fluoroaliphatic group-containing monomer. It is preferably 5% by mass or more, more preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 5% by mass.

  The mass average molecular weight of the polymer A used in the present invention is preferably 1,000,000 or less, more preferably 500,000 or less, and further preferably 5,000 or more and 50,000 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 employed when producing the polymer A is not particularly limited, but the method described in [0035] to [0041] of JP-A No. 2004-46038 is preferably used.

  The polymer A preferably has a polymerizable group as a substituent in order to fix the alignment state of the rod-like liquid crystal compound.

  Specific examples that are preferably used in the present invention as the polymer A 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 TSK Gel GMHxL, TSK Gel G4000 HxL, TSK Gel G2000 HxL (whichever Also, the mass average molecular weight is expressed in terms of polystyrene by solvent THF and differential refractometer detection using a GPC analyzer using a column of Tosoh Corporation's trade name).

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

  The preferred range of the content of the polymer A in the first optically anisotropic layer-forming composition varies depending on its use, but 0 in the composition (a composition excluding the solvent in the case of a coating solution). 0.005 to 8% by mass is preferable, 0.01 to 5% by mass is more preferable, and 0.05 to 1% by mass is even more preferable. If the amount of the repeating unit derived from the fluoroaliphatic group-containing monomer is less than 0.005% by mass, the effect is insufficient, and if it exceeds 8% by mass, the coating film may not be sufficiently dried. The performance as an optical compensation film (for example, uniformity of retardation, etc.) may be adversely affected.

[Onium salt]
The first optically anisotropic layer preferably contains at least one onium salt. The onium salt contributes to the vertical alignment of the molecules of the rod-like liquid crystal compound on the alignment film interface side. Examples of the onium salts include ammonium salts containing nitrogen atoms, sulfonium salts containing sulfur atoms, phosphonium salts containing phosphorus atoms, and the like.

The onium salt is preferably a quaternary onium salt, more preferably a quaternary ammonium salt.
A quaternary ammonium salt is generally a tertiary amine (eg, trimethylamine, triethylamine, tributylamine, triethanolamine, N-methylpyrrolidine, N-methylpiperidine, N, N-dimethylpiperazine, triethylenediamine, N, N , N ′, N′-tetramethylethylenediamine, etc.) or nitrogen-containing heterocycle (pyridine ring, picoline ring, 2,2′-bipyridyl ring, 4,4′-bipyridyl ring, 1,10-phenanthroline ring, quinoline ring, An oxazole ring, a thiazole ring, an N-methylimidazole ring, a pyrazine ring, a tetrazole ring, and the like) are obtained by alkylation (Mentstock reaction), alkenylation, alkynylation, or arylation.

As the quaternary ammonium salt, a quaternary ammonium salt composed of a nitrogen-containing heterocyclic ring is preferable, and a quaternary pyridinium salt is particularly preferable.
More specifically, the quaternary ammonium salt is preferably selected from quaternary pyridinium salts represented by the following general formula (3a) or a general formula (3b) described later.

In the formula (3a), R ⁸ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group, D represents a hydrogen bonding group, and m represents 1 to 3 X ⁻ represents an anion.

First, the general formula (3a) will be described.
The alkyl group represented by R ⁸ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. These may be linear, branched or cyclic. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, neopentyl, cyclohexyl, adamantyl. Group and cyclopropyl group.

  Examples of the substituent of the alkyl group include the following. C2-C18 (preferably C2-C8) substituted or unsubstituted alkenyl group (for example, vinyl group); C2-C18 (preferably C2-8) substituted or unsubstituted alkynyl Group (for example, ethynyl group); substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl group, naphthyl group); halogen atom (for example, F, Cl, Br, etc.); Preferably a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms (for example, methoxy group or ethoxy group); a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, biphenyloxy group, p-methoxyphenoxy group); substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (for example, methylthio group, ethylthio group) A substituted or unsubstituted arylthio group having 6 to 10 carbon atoms (for example, phenylthio group); a substituted or unsubstituted acyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (for example, an acetyl group or a propionyl group) );

  C1-C18 (preferably C1-C8) substituted or unsubstituted alkylsulfonyl group or arylsulfonyl group (for example, methanesulfonyl group, p-toluenesulfonyl group); C2-C18 (preferably carbon) A substituted or unsubstituted acyloxy group (for example, acetoxy group, propionyloxy group) having 2 to 8 carbon atoms; a substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms (preferably having 2 to 8 carbon atoms) (for example, A methoxycarbonyl group, an ethoxycarbonyl group); a substituted or unsubstituted aryloxycarbonyl group having 7 to 11 carbon atoms (for example, a naphthoxycarbonyl group); an unsubstituted amino group, or a carbon number of 1 to 18 (preferably having a carbon number) 1-8) substituted amino groups (for example, methylamino group, dimethylamino group, diethylamino group) Anilino group, methoxyphenylamino group, chlorophenylamino group, pyridylamino group, methoxycarbonylamino group, n-butoxycarbonylamino group, phenoxycarbonylamino group, methylcarbamoylamino group, ethylthiocarbamoylamino group, phenylcarbamoylamino group, acetylamino Group, ethylcarbonylamino group, ethylthiocarbamoylamino group, cyclohexylcarbonylamino group, benzoylamino group, chloroacetylamino group, methylsulfonylamino group);

  C1-C18 (preferably C1-C8) substituted or unsubstituted carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, n-butylcarbamoyl group, tert-butylcarbamoyl group) , Dimethylcarbamoyl group, morpholinocarbamoyl group, pyrrolidinocarbamoyl group); unsubstituted sulfamoyl group, or substituted sulfamoyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (for example, methylsulfamoyl group, phenyl) Sulfamoyl group); cyano group; nitro group; carboxy group; hydroxyl group; heterocyclic group (for example, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring) , Piperidine ring, pyro Jin ring, morpholine ring, sulfolane ring, furan ring, thiophene ring, pyrazole ring, pyrrole ring, chroman ring, a coumarin ring). The substituent for the alkyl group is particularly preferably an aryloxy group, an arylthio group, an arylsulfonyl group, or an aryloxycarbonyl group.

The alkenyl group represented by R ⁸ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, such as a vinyl group. , Allyl group, 1-propenyl group, 1,3-butadienyl group and the like.
As the substituent for the alkenyl group, those exemplified as the substituent for the alkyl group are preferable.

The alkynyl group represented by R ⁸ is preferably a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, such as an ethynyl group. , 2-propynyl and the like. As the substituent for the alkynyl group, those exemplified as the substituent for the alkyl group are preferable.

The aralkyl group represented by R ⁸ is preferably a substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, such as a benzyl group, a methylbenzyl group, a biphenylmethyl group, or a naphthylmethyl group. Examples of the substituent for the aralkyl group include those exemplified as the substituent for the alkyl group.

The aryl group represented by R ⁸ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a fluorenyl group. As the substituent for the aryl group, those exemplified as the substituent for the alkyl group are preferable. In addition to these, an alkyl group (for example, a methyl group, an ethyl group, etc.), an alkynyl group, and a benzoyl group are also preferable.

The heterocyclic group represented by R ⁸ is a 5- or 6-membered saturated or unsaturated heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, and examples thereof include oxazole Ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, sulfolane ring, furan ring, thiophene ring, pyrazole ring, pyrrole ring , Chroman ring, and coumarin ring. The heterocyclic group may be substituted, and as the substituent in that case, those exemplified as the substituent of the alkyl group are preferable. As the heterocyclic group represented by R ⁸ , a benzoxazole ring and a benzothiazole ring are particularly preferable.

R ⁸ is preferably a substituted or unsubstituted alkyl group, aralkyl group, aryl group or heterocyclic group.

  D represents a hydrogen bonding group. Hydrogen bonds exist between electronegative atoms (eg, O, N, F, Cl) and hydrogen atoms covalently bonded to electronegative atoms as well. As a theoretical interpretation of hydrogen bonding, for example, H.H. Unneyama and K.M. There are reports in Morokuma, Journal of American Chemical Society, Vol. 99, pp. 1316-1332, 1977. Specific examples of hydrogen bonding include J.I. N. Examples include Israes Ativiri, Yasuo Kondo, Hiroyuki Oshima, Intermolecular Force and Surface Force, McGraw Hill, 1991, page 98, FIG. Specific examples of hydrogen bonding include, for example, G.I. R. Examples include those described in Desiraju, Angewent Chemistry International Edition England, Vol. 34, p. 2311, 1995.

  Preferred hydrogen bonding groups include mercapto groups, hydroxy groups, amino groups, carbonamido groups, sulfonamido groups, acid amide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups, nitrogen-containing heterocyclic groups (for example, imidazolyl). Group, benzimidazolyl group, pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinimide group, phthalimide group, maleimide group, uracil group, thiouracil Group, barbituric acid group, hydantoin group, maleic hydrazide group, isatin group, uramil group and the like. More preferred hydrogen bonding groups include amino group, carbonamido group, sulfonamido group, ureido group, carbamoyl group, carboxyl group, sulfo group and pyridyl group, and particularly preferred are amino group, carbamoyl group, A pyridyl group can be mentioned.

The anion represented by X ⁻ may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluorine ion, chlorine ion, bromine ion, iodine ion), sulfonate ion (eg, methanesulfone). Acid ion, trifluoromethanesulfonic acid ion, methylsulfuric acid ion, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene Disulfonate ions, etc.), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, phosphate ions (for example, hexafluorophosphate ions), hydroxide ions, etc. .
X ⁻ is preferably a halogen anion, a sulfonate ion, or a hydroxide ion. X ⁻ need not be a monovalent anion and may be a divalent or higher anion. In such a case, the ratio of the cation to the anion in the compound need not be 1: 1, It is determined.

  In the general formula (3a), m is preferably 1.

Next, the general formula (3b) will be described.

In formula (3b), R ⁹ and R ¹⁰ each represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group, and X ⁻ represents an anion.
The substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group represented by R ⁹ and R ¹⁰ respectively is represented by R ⁸ in the general formula (3a). It is synonymous with a group, and its preferable range is also the same. X ^- anion represented by the In the general formula (3a), X ^- has the same meaning as anion represented by, and the preferable ranges thereof are also the same. As described above, X ⁻ need not be a monovalent anion but may be a divalent or higher anion. In such a case, the ratio of the cation to the anion in the compound should be 1: 2. It is not determined.

  Specific examples of the quaternary pyridinium salt represented by the general formula (3a) or (3b) and other onium salts preferably used in the present invention are shown below, but the onium salts used in the present invention are shown below. It is not limited.

  The preferable content of the onium salt in the first optically anisotropic layer varies depending on the type of the onium salt, but usually 0.01 to 10 with respect to the content of the liquid crystal compound used in combination. The content is preferably mass%, more preferably 0.05 to 7 mass%, and still more preferably 0.05 to 5 mass%. Two or more kinds of onium salts may be used. In such a case, the total content of all kinds of onium salts to be used is preferably within the above range.

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

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

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

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

  In the present invention, the first optically anisotropic layer is prepared by, for example, dissolving and / or dispersing a liquid crystalline compound and additives such as a polymerization initiator and an alignment controller added as required in a solvent. The coating liquid can be formed by coating on a support. It is preferable to form an alignment film on a support and apply the coating solution on the surface of the alignment film. 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.

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

  A die coating method is preferably used for forming the first optically anisotropic layer, and a coating method using a slide coater or a slot die coater is particularly preferable. For example, the coating methods described in JP-A No. 2004-290775, JP-A No. 2004-290776, JP-A No. 2004-358296, JP-A No. 2005-13989, and the like can be used.

Next, as described above, after the composition is applied to the surface of the support or the alignment film, the molecules of the liquid crystalline compound are aligned (preferably vertical alignment for rod-like liquid crystalline molecules), and the molecules are aligned. To form an optically anisotropic layer. The alignment temperature can be determined in consideration of the transition temperature of the liquid crystal compound to be used, the desired alignment state, and the like. The immobilization is preferably carried out by a polymerization reaction or a crosslinking reaction of liquid crystalline molecules or a polymerizable monomer that is optionally added to the composition. It is preferable to use ultraviolet rays for light irradiation for polymerization. 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 formed optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and still more preferably 1 to 5 μm.

[Alignment film]
An alignment film may be used for producing the first optically anisotropic layer. The alignment film has a function of defining the alignment direction of molecules of a liquid crystal compound, preferably a rod-like liquid crystal compound.
In addition, when the alignment layer side vertical alignment agent such as the onium salt and the air interface vertical alignment agent such as the fluorine-based polymer described above are contained, the molecules of the rod-like liquid crystal compound can be obtained without using the vertical alignment film. Since the vertical alignment can be stably performed, the vertical alignment film is not essential for forming the optically anisotropic layer. However, by applying the first composition for forming an optically anisotropic layer on the surface of the alignment film containing a hydrophilic group, the alignment uniformity of the liquid crystalline composition can be improved, or the polymer substrate and the optical film Since the adhesion between the anisotropic layer can be improved, it is preferable to use an alignment film. Further, if the molecules of the rod-like liquid crystal compound are aligned and fixed in the alignment state, the alignment film plays the role and can be removed. For example, it is possible to produce a polarizing plate having an optically anisotropic layer by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto a polarizer.

  The alignment film is an organic compound (for example, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodget 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 can be rubbed if necessary. In principle, the polymer used for the alignment film has a molecular structure having a function of aligning the liquid crystal compound.
In the present invention, in addition to the function of aligning the liquid crystalline compound, the cross-linking having a function of binding a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning the liquid crystalline compound. It is preferable to introduce a functional functional group into the side chain.
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.

  Examples of the polymer include, for example, methacrylate polymer, styrene polymer, polyolefin, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide) described in paragraph No. [0022] of JP-A-8-338913. , Polyester, polyimide, vinyl acetate polymer, 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. .

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

  The modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine atoms Substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy) and the like can be mentioned. As specific examples of these modified polyvinyl alcohol compounds, for example, paragraph numbers [0022] to [0145] in JP-A No. 2000-155216 and paragraph numbers [0018] to [0018] in JP-A No. 2002-62426 are described. [0022] and the like.

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 a function of aligning the liquid crystalline 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 film can be remarkably improved by introducing the crosslinkable functional group into the alignment film polymer.
The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specifically, for example, those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216, and the like can be mentioned.

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

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

  The alignment film can basically be formed by applying the above-mentioned polymer as an alignment film forming material and a support containing a crosslinking agent, followed by drying by heating (crosslinking) and, if necessary, rubbing treatment. it can. As described above, the crosslinking reaction may be carried out at any time after coating on the 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 by mass is water: methanol greater than 0 and 99 or less: less than 100, preferably 1 or more, and more preferably greater than 0 and 91 or less: less than 100, 9 or more. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an orientation film and also an optically anisotropic layer reduces remarkably.

  The alignment film is preferably applied by spin coating, dip coating, curtain coating, extrusion coating, rod coating, or roll coating. A rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heat drying can be performed at 20 to 110 degrees. In order to form sufficient cross-linking, 60 ° to 100 ° is preferable, and 80 ° to 100 ° is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes.

  After aligning the liquid crystalline compound on the alignment film, if necessary, the alignment film polymer is reacted with the polyfunctional monomer contained in the optically anisotropic layer, or the alignment film polymer is formed using a crosslinking agent. It may be cross-linked. The thickness of the alignment film is preferably in the range of 0.1 to 10 μm.

  In order to uniformly align the liquid crystalline compound, it is preferable to control the alignment direction with an alignment film. In addition, after aligning a liquid crystalline compound using an alignment film, the liquid crystalline compound is fixed in the alignment state to form an optically anisotropic layer, and only the optically anisotropic layer is formed as a polymer film (or a support). ) May be transferred onto. That is, even if an alignment film is used during the production of the optically anisotropic layer, the alignment film is not necessarily a constituent member of the optical compensation film of the present invention.

[Support]
The first optically anisotropic layer contained in the optical compensation film of the present invention may be formed on a support. The first optical anisotropic layer may be formed on the surface using the above-mentioned second optical anisotropic layer (for example, cellulose acylate film) as the support, or the first optical anisotropic layer may be formed on the temporary support. After forming on one optically anisotropic layer, it may be transferred onto the second optically anisotropic layer, or an optically isotropic film may be used as a support. When the first optically anisotropic layer is formed on an optically isotropic support, the support may be removed or left when used in a liquid crystal display device. The laminate with the second optically anisotropic layer can be incorporated into a liquid crystal display device or the like as an optical compensation film.

The support can also be used as a protective film for a polarizing film. The support preferably has a light transmittance of 80% or more.

  Examples of the polymer film as the support include cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyacrylate and polymethacrylate films. A cellulose ester film is preferred, an acetyl cellulose film is more preferred, and a triacetyl cellulose film is most preferred. 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 40 to 200 μm. In order to improve adhesion between the support and the layer (adhesive layer, vertical alignment film or optically anisotropic layer) provided thereon, the support is subjected to surface treatment (for example, glow discharge treatment, corona discharge treatment, ultraviolet light (UV ) Treatment, flame treatment). An adhesive layer (undercoat layer) may be provided on the support. In addition, it is also preferable that the support is a film of a polymer or the like having a polymerizable group because adhesion with the optically anisotropic layer is improved. 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, an average particle size is about 10-100 nm. It is preferable to use what formed the polymer layer which mixed inorganic particle 5%-40% by solid content weight ratio on the one side of the support body by the application | coating or co-casting with a support body.

  As a substantially isotropic support (hereinafter sometimes referred to as a low Re film), the in-plane retardation (Re) is preferably 0 to 10 nm, more preferably 0 to 5 nm, and 0 Most preferably, it is ˜3 nm. The retardation in the thickness direction (Rth) is preferably -20 nm to 20 nm, preferably -15 nm to 15 nm, and most preferably -10 nm to 10 nm. The wavelength dispersion is preferably such that the ratio of Re400 / Re700 is less than 1.2. Furthermore, the haze of the low Re film is preferably 1.0% or less, and more preferably 0.8% or less.

Hereinafter, the polarizing plate of the present invention to which the optical compensation film of the present invention is added will be described in detail.
[Polarizer]
The polarizing plate of the present invention has at least the optical compensation film of the present invention and a polarizing film.
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.

  As the polymer used for the base film of the polarizing film, a polyvinyl alcohol (hereinafter referred to as PVA) polymer is generally used. As the dichroic substance, iodine or a dichroic dye is used alone or in combination. PVA is usually a saponified polyvinyl acetate, but may contain components copolymerizable with vinyl acetate such as unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, and vinyl ethers. I do not care. In addition, modified PVA containing an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, or the like can also be used. The degree of saponification of PVA is not particularly limited, but is preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% from the viewpoints of solubility, polarization, heat resistance, moisture resistance, and the like. The degree of polymerization of PVA is not particularly limited, but is preferably from 1000 to 10,000, particularly preferably from 1500 to 5000, from the viewpoints of film strength, heat resistance, moisture resistance, stretchability, and the like. Moreover, it does not specifically limit about the syndiotacticity of PVA, It can also take arbitrary values according to the objective.

  In order to prepare a polarizing film by dyeing and stretching PVA, a method in which a PVA film as a raw fabric is stretched dry or wet and then immersed in a solution of iodine or dichroic dye, iodine or dichroic dye There are a method of stretching and orienting a PVA film in the above solution, a method of stretching and orienting a PVA film in iodine or a dichroic dye and then wet or dry. Moreover, when forming a PVA raw fabric by a solution casting method, a method of previously containing a dichroic substance in the PVA solution can be used.

  A manufacturing method by wet stretching of a typical polarizing plate will be described below. First, the raw fabric PVA film is pre-swelled with an aqueous solution. Subsequently, it is immersed in the solution of a dichroic substance, and a dichroic substance is adsorbed. Further, it is uniaxially stretched in the traveling direction in an aqueous solution of a boron compound such as boric acid. If necessary, a color adjustment bath, a curing bath or the like may be provided after this. When it is dried to some extent, a protective film is bonded using an adhesive such as PVA. Furthermore, it dries and a polarizing plate is obtained.

  Various organic solvents, inorganic salts, plasticizers, boric acids and the like may be added to the pre-swelled solution in the aqueous solution.

  As an example of the case where iodine is used as the dichroic substance, an iodine-potassium iodide aqueous solution is used as the staining liquid. Iodine is preferably 0.1 to 20 g / liter, potassium iodide is preferably 1 to 100 g / liter, and the weight ratio of iodine and potassium iodide is preferably 1 to 100. The dyeing time is preferably 30 to 5000 seconds, and the liquid temperature is preferably 5 to 50 ° C. It is also preferable to include a compound that crosslinks PVA such as a boron compound in the dyeing solution. The boron compound in the stretching bath is particularly preferably boric acid. The boric acid concentration is preferably 1 to 200 g / liter, more preferably 10 to 120 g / liter. In addition to the boron compound, the stretching bath can contain an inorganic salt such as potassium iodide, various organic solvents, or a dichroic dye. In addition to the dichroic dye, an inorganic salt such as potassium iodide, a boron compound, and the like are contained in the color adjustment bath and the curing bath as necessary.

  The stretching process of PVA is generally a method in which tension is applied in the traveling direction of the continuous film and the film is stretched and oriented in the traveling direction as exemplified above, but the film is stretched by stretching means such as a so-called tenter method. A method of applying tension in the width direction and orienting in the width direction is also applicable. The stretching is preferably performed 3 times or more in a uniaxial direction, and more preferably 4.5 times or more. Biaxial stretching may be performed depending on the purpose of use of the polarizing film. Although the film thickness after extending | stretching is not specifically limited, 5-100 micrometers is preferable from a viewpoint of a handleability, durability, and economical efficiency, and 10-40 micrometers is more preferable. The temperature during stretching varies depending on the stretching conditions, but is usually 10 to 250 ° C. When dry stretching at a temperature of 100 ° C. or higher, it is preferably performed in an inert gas atmosphere such as nitrogen. Moreover, it is preferable to perform a crystallization treatment at a temperature of 100 ° C. or higher before dyeing a previously stretched film.

  As the dyeing method, not only the immersion method exemplified above, but also any means such as application or spraying of iodine or a dye solution is possible. In addition to the liquid layer adsorption described above, adsorption by donation can be performed as necessary. It is also preferable to dye with a dichroic dye. Specific examples of the dichroic dye include dye compounds such as azo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes and anthraquinone dyes. I can give you. A water-soluble one is preferred, but not limited thereto. Further, it is preferable that a hydrophilic substituent such as a sulfonic acid group, an amino group, or a hydroxyl group is introduced into these dichroic molecules.

  Typical examples of dichroic molecules include C.I. Eye. direct. Yellow 12, sea. Eye. direct. Orange 39, sea. Eye. direct. Orange 72, sea. Eye. direct. Red 28, Sea. Eye. direct. Red 39, Sea. Eye. direct. Red 79, Sea. Eye. direct. Red 81, Sea. Eye. direct. Red 83, Sea. Eye. direct. Red 89, Sea. Eye. direct. Violet 48, C.I. Eye. direct. Blue 67, Sea. Eye. direct. Blue 90, Sea. Eye. direct. Green 59, Sea. Eye. Acid. Red 37 and the like, and further, JP-A-1-161202, JP-A-1-172906, JP-A-1-172907, JP-A-1-183602, JP-A-2000-48105, JP-A-2000-65205, Examples thereof include the dyes described in JP-A-7-261024. In particular, Sea. Eye. direct. Red 28 (Congo Red) has long been known as preferred for this application. These dichroic molecules are used as free acids or alkali metal salts, ammonium salts, and salts of amines.

  By blending two or more of these dichroic molecules, it is possible to produce polarizers having various hues. As a polarizing element or polarizing plate, a compound (pigment) that exhibits black when the polarization axes are orthogonal to each other, or a compound in which various dichroic molecules are blended so as to exhibit black is excellent in terms of both the single plate transmittance and the polarization.

  From the viewpoint of increasing the heat resistance and moisture resistance of the polarizing film, it is preferable to include an additive that crosslinks PVA in the manufacturing process of the polarizing film. As the crosslinking agent, those described in US Reissue Patent No. 232897 can be used, but boric acid and borax are preferably used practically. In addition, it is known that the polarizing film contains a metal salt such as zinc, cobalt, zirconium, iron, nickel, manganese, etc., because it is known to improve durability. These crosslinking agents and metal salts may be contained in any of the above-described pre-swelling bath, dichroic material dyeing bath, stretching bath, curing bath, color adjusting bath, etc., and the order of the steps is particularly limited. Not. The adhesive that bonds the protective film and the polarizing film is not particularly limited, and any known adhesive such as PVA, modified PVA, urethane, or acrylic can be used. The thickness of the adhesive layer is preferably from 0.01 to 20 μm, more preferably from 0.1 to 10 μm.

  The polarizing film generally has a protective film. In the present invention, when the second optical anisotropic layer is made of a polymer film such as a cellulose acylate film, the second optical anisotropic layer may be used as a protective film for the polarizing film. When the first optically anisotropic layer is formed on a transparent support made of a polymer film or the like, the transparent support may be used as a protective film for the polarizing film. As a protective film for the polarizing film, it is preferable to use a cellulose ester film that has low birefringence, transparency, appropriate moisture permeability, dimensional stability and the like, and has high optical isotropy.

  The preferable manufacturing method of the polarizing plate of this invention includes the process of laminating | stacking a polarizing film and an optical compensation film continuously in a respectively long state. The long polarizing plate is cut according to the screen size of the liquid crystal display device used.

  The polarizing film generally has a protective film on both surfaces. The optical compensation film of the present invention can function as a protective film for the polarizing film. In such a case, it is not necessary to separately bond a protective film to the surface of the polarizing film to be bonded to the surface of the optical compensation film. . The polarizing film generally has a protective film. In the polarizing plate of the present invention, only an isotropic adhesive layer and / or a substantially isotropic transparent protective film is included between the polarizing film and the optical compensation film of the present invention. Is preferred. The substantially isotropic transparent protective film (protective film for polarizing film) is specifically a film having an in-plane retardation of 0 to 10 nm and a retardation in the thickness direction of -20 to 20 nm. A film containing cellulose acylate or cyclic polyolefin is preferred. Examples of the cellulose acylate or cyclic polyolefin that can be used for the transparent protective film are the same as those of the polymer film that can be used as the support for the first optically anisotropic layer. Moreover, as an adhesive which can form an isotropic adhesive bond layer, the adhesive agent etc. which consist of a polyvinyl alcohol-type adhesive agent, polyester-type urethane, and an isocyanate type crosslinking agent are mentioned.

  In the first aspect of the polarizing plate of the present invention, the first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and 2 is a polarizing plate in which the direction of the slow axis of the optically anisotropic layer and the direction of the absorption axis of the polarizing film are substantially orthogonal; and the second mode of the polarizing plate of the present invention is: The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and the slow axis of the second optical anisotropic layer In the polarizing plate, the direction and the direction of the absorption axis of the polarizing film are substantially parallel. When the second optically anisotropic layer is made of a stretched polymer film, the direction of the slow axis is determined by the stretch direction.

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

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

The polarizing plate in the present invention is preferably used for a reflective, transflective, and transmissive liquid crystal display device. 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 usually 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. As the polarizing plate, the polarizing plate of the present invention can be used. In such a case, the retardation plate may not be separately provided.
The transflective liquid crystal display device includes a liquid crystal cell, a polarizing plate disposed on the viewer side of the liquid crystal cell, and at least one retardation plate disposed between the polarizing plate and the liquid crystal cell. And at least one transflective layer disposed behind the liquid crystal layer as viewed from the viewer, and at least one retardation plate and polarizing plate behind the transflective layer as viewed from the viewer And 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. Both polarizing plates may be the polarizing plate of the present invention, or only one of them may be the polarizing plate of the present invention. When the polarizing plate of the present invention is arranged, a retardation plate may not be separately arranged between the liquid crystal cell and the polarizing plate of the present invention.

The mode of the liquid crystal cell is not particularly limited, but is preferably an IPS mode or an FFS mode.
In an IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. In the IPS mode, black is displayed when no electric field is applied, and the transmission axes of the pair of upper and lower polarizing plates are orthogonal. A method of reducing leakage light at the time of black display in an oblique direction and improving a viewing angle using an optical compensation film is disclosed in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522. No. 11-133408, No. 11-305217, No. 10-307291, and the like.

  For example, the polarizing plate of the first aspect includes a liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display ( For example, when used in a liquid crystal display device having an IPS mode liquid crystal cell), the first optical anisotropic layer and the second optical anisotropy are formed on the outside of one of the pair of substrates from the substrate side. The polarizing plate is arranged so that the layer and the polarizing film are in this order, and the slow axis of the second optically anisotropic layer is substantially parallel to the major axis direction of the liquid crystal molecules during black display. In addition, a second polarizing film can be further disposed outside the other substrate. In this case, the absorption axes of both polarizing films are arranged to be orthogonal to each other.

  Further, the polarizing plate of the second aspect includes a liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display ( For example, when used in a liquid crystal display device having an IPS mode liquid crystal cell), the first optical anisotropic layer and the second optical anisotropy are formed on the outside of one of the pair of substrates from the substrate side. The polarizing plate is arranged so that the layer and the polarizing film are in this order, and the slow axis of the second optically anisotropic layer and the major axis direction of the liquid crystal molecules during black display are substantially perpendicular to each other. A second polarizing film can be further disposed outside the other substrate. Also in this case, the absorption axes of both polarizing films are arranged to be orthogonal to each other.

  In any of the above embodiments, a substantially isotropic adhesive layer between the second polarizing film and the substrate, and / or a substantially isotropic transparent protective film (protecting the polarizing film) It is preferable that only a film) is included. The substantially isotropic transparent protective film specifically has an in-plane retardation of 0 to 10 nm and a thickness direction retardation of -20 to 20 nm. For example, cellulose acylate having such optical properties Or the film containing cyclic polyolefin is preferable. Examples of the cellulose acylate or cyclic polyolefin that can be used for the transparent protective film are the same as those of the polymer film that can be used as the support for the first optically anisotropic layer. Moreover, as an adhesive which can form an isotropic adhesive bond layer, the adhesive agent etc. which consist of a polyvinyl alcohol-type adhesive agent, polyester-type urethane, and an isocyanate type crosslinking agent are mentioned.

  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.

<Formation of Second Optically Anisotropic Layer>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution. The solution was filtered using a filter paper (No. 63, manufactured by Advantech) having a retained particle size of 4 μm and a drainage time of 35 seconds at 0.5 MPa (5 kg / cm ² ) or less.

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

  In another mixing tank, 16 parts by mass of retardation increasing agent A-1 which is the following discotic compound, 8 parts by mass of retardation increasing agent B which is the following rod-like compound, silicon dioxide fine particles (average particle size: 0.1 μm) ) 0.28 parts by mass, 80 parts by mass of methylene chloride and 20 parts by mass of methanol were added and stirred while heating to prepare Solution A. 40 parts by mass of the solution A was mixed with 474 parts by mass of the cellulose acetate solution, and stirred well to prepare a dope.

Retardation raising agent A-1

  The obtained dope was cast using a band casting machine. A film having a residual solvent amount of 15% by mass was stretched transversely at a stretch ratio of 20% using a tenter under the conditions of 130 ° C., held at 50 ° C. for 30 seconds with the stretched width, and then clipped to remove cellulose. An acetate film was prepared. The residual solvent amount at the end of stretching was 5% by mass, and further dried to prepare a film with the residual solvent amount being less than 0.1% by mass.

  The cellulose acetate film F1 thus obtained had a thickness of 80 μm. Using the automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the dependency of Re on the incident angle of light was measured for the polymer substrate thus produced, and Re was 62 nm and Rth was 190 nm. I found out. Moreover, it was 0.65% when the haze measurement was performed with the Nippon Denshoku Industries Co., Ltd. haze meter (NDH-2000). The cellulose acetate film F1 was found to satisfy the characteristics required for the second optically anisotropic layer.

  As shown in Table 1, the cellulose acetate films F2 to F6 and FH1 to F1 were used in the same manner as the cellulose acetate film F1, except that the type, addition amount and stretching ratio of the retardation increasing agent A-1 and retardation increasing agent B were changed. FH3 was produced and the haze was measured in the same manner. Table 1 shows the results.

Retardation raising agent A-2

(Preparation of the first optical anisotropic layer)
The prepared second optically anisotropic layer (cellulose acetate film F1) was subjected to surface saponification treatment, and an alignment film coating solution having the following composition was applied to the surface thereof with a wire bar coater at 20 ml / m ² . A 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 to obtain an alignment film.
Composition of alignment film coating liquid Modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight

Modified polyvinyl alcohol

  A coating solution containing a rod-like liquid crystal compound having the following composition was continuously applied onto the prepared alignment film with a # 5.0 wire bar. The conveyance speed of the film was 20 m / min. The solvent was dried in a step of continuously heating from room temperature to 80 ° C., and then heated in a drying zone at 80 ° C. for 90 seconds to align the rod-like liquid crystal compound. Subsequently, the temperature of the film was maintained at 80 ° C., and the orientation of the liquid crystal compound was fixed by UV irradiation to form a first optical anisotropic layer. Subsequently, the film prepared in a 1.5 mol / L sodium hydroxide aqueous solution at 55 ° C. was immersed for 2 minutes, and then immersed in water to sufficiently wash away sodium hydroxide. Then, after being immersed for 1 minute in 5 mmol / L sulfuric acid aqueous solution of 35 degreeC, it was immersed in water and the dilute sulfuric acid aqueous solution was fully washed away. Finally, the sample was thoroughly dried at 120 ° C. Thus, an optical compensation film in which the first and second optically anisotropic layers were laminated was produced. Moreover, it was 0.61% when the haze measurement was performed with the Nippon Denshoku Industries Co., Ltd. haze meter (NDH-2000).

Composition of coating liquid containing rod-shaped liquid crystal compound ――――――――――――――――――――――――――――――――――――
The following rod-like liquid crystalline compound 100 parts by weight Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by weight Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by weight Polymer A (P-33) 0.2 parts by weight Onium salt (21) 1 part by weight Methyl ethyl ketone 172 parts by weight ――――――――――――――――――――――――――――――――― ―――

Rod-shaped liquid crystal compound

  Only the optically anisotropic layer containing the rod-like liquid crystalline compound (first optically anisotropic layer) is peeled off from the produced optical compensation film, and an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.) ) Was used to measure optical properties. Re of only the optically anisotropic layer measured at a wavelength of 590 nm was 0 nm, and Rth was −263 nm. It was also confirmed that an optically anisotropic layer was formed in which rod-like liquid crystal molecules were aligned substantially perpendicular to the layer surface.

<Preparation of Polarizing Plate 1-1>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. The surface on which the first optical anisotropic layer of the produced optical compensation film is not formed on one surface of the polarizing film (that is, the back surface of the cellulose acylate film F1 which is the second optical anisotropic layer) ) Is continuously bonded to the other surface of the cellulose triacetate film (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) using a polyvinyl alcohol-based adhesive. -1 was produced. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

<Production of low Re film>
(Preparation of cellulose acetate solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution A.
Composition of cellulose acetate solution A ――――――――――――――――――――――――――――――――――――
Cellulose acetate with an acetyl substitution degree of 2.94 100.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass ――――――――――――― ――――――――――――――――――――――

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

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

Optical anisotropy reducing agent

Chromatic dispersion modifier

(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. The mass ratio of the compound that reduces optical anisotropy and the wavelength dispersion adjusting agent to cellulose acetate in the above composition was 12% and 1.2%, respectively. The film was peeled from the band with a residual solvent amount of 30% and dried at 140 ° C. for 40 minutes to produce a long cellulose acetate film T0 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. Moreover, it was 0.72% when the haze measurement was performed with the Nippon Denshoku Industries Co., Ltd. haze meter (NDH-2000).

<Preparation of Polarizing Plate 1-2>
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. A commercially available cellulose acetate film (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) obtained by saponifying the above-mentioned low Re film on one side of the polarizing film and a polyvinyl alcohol adhesive on the other side. Using them, they were continuously bonded together to produce a polarizing plate 1-2.

<Preparation of Polarizing Plate 1-3>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. A commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was subjected to saponification treatment, and a polarizing plate 1-3 was formed on a polarizing film by using a polyvinyl alcohol adhesive. The haze of the commercially available cellulose acylate was 0.60%.

<Production of liquid crystal display device>
A liquid crystal cell was taken out from the liquid crystal television TH-32LX500 (manufactured by Matsushita Electric Industrial Co., Ltd.), and the polarizing plate and the optical film which were pasted on the viewer side and the backlight side were peeled off. In this liquid crystal cell, when no voltage was applied and during black display, the liquid crystal molecules were aligned substantially in parallel between the glass substrates, and the slow axis direction was horizontal to the screen.

  The produced polarizing plates (1-1 and 1-2) were bonded to the upper and lower glass substrates of the parallel alignment cell using an adhesive. At this time, 1-1 is disposed on the polarizing plate on the backlight side, 1-2 is disposed on the viewer side, and the first optical anisotropic layer included in the polarizing plate 1-1 is the glass on the backlight side. It bonded so that the cellulose acetate film contained in the polarizing plate 1-2 might contact the glass substrate by the side of a viewer so that it might contact with a board | substrate. Moreover, the absorption axis of the polarizing plate 1-1 and the slow axis of the liquid crystal cell were orthogonal to each other, and the absorption axes of the polarizing plate 1-1 and the polarizing plate 1-2 were orthogonal to each other. The liquid crystal cell on which the polarizing plate was bonded in this way was again incorporated into the liquid crystal television TH-32LX500. Thus, liquid crystal display device L1 was produced and the front contrast was measured using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM).

  A liquid crystal display device was produced using the film produced by the liquid crystal display device L1 except that the angle formed by the absorption axis of the polarizing film and the slow axis of the second optically anisotropic layer was 0 °. It was 712 when the front contrast was measured using the measuring machine (EZ-Contrast160D, ELDIM company make).

[Reference Example 1 (S1)]
A liquid crystal display device was prepared in the same manner as in Example 1 except that the polarizing plates 1-1 and 1-2 were bonded to the upper and lower glass substrates of the parallel alignment cell using an adhesive. It was 696 when produced and the front contrast was measured.

As shown in Table 2, the type of cellulose acylate film used as the second optically anisotropic layer, the type and / or addition amount of polymer A used in forming the first optically anisotropic layer, and the type of onium salt And / or except that the addition amount was changed, respectively, in the same manner as described above, an optical compensation film and a polarizing plate were respectively prepared, and each of the prepared polarizing plates was used instead of the polarizing plate 1-1. In the same manner as the liquid crystal display device L1, liquid crystal display devices L2 to L5 and LH1 to LH3 were produced.
About each of the produced liquid crystal display device, the liquid crystal display device was produced similarly to the haze measurement and contrast Example, and front contrast was measured.

Claims (14)

It includes at least a first optical anisotropic layer and a second optical anisotropic layer, the in-plane retardation of the first optical anisotropic layer is 0 to 10 nm, and the retardation in the thickness direction is −400. An optical compensation film having an in-plane retardation of the second optically anisotropic layer of 20 to 150 nm and a retardation in the thickness direction of 100 to 300 nm. The haze of the anisotropic layer is set to Hz (B) (%), and the haze made of a laminate of the first optical anisotropic layer and the second optical anisotropic layer is set to Hz (B + L) (%). Then, an optical compensation film satisfying the following relational expressions (1) to (3):
(1) 0 <Hz (B + L) <1.0%
(2) 0 <Hz (B) <1.0%
(3) Hz (B + L) / Hz (B) <1.3. 2. The optical compensation film according to claim 1, wherein the second optically anisotropic layer is made of a cellulose acylate film stretched by a transverse stretching method, a longitudinal stretching method, a simultaneous biaxial stretching method, or a sequential biaxial stretching method. The first optically anisotropic layer is made of a composition containing a rod-like liquid crystal compound, and the molecules of the rod-like liquid crystal compound are aligned substantially perpendicular to the layer surface in the layer, The optical compensation film according to claim 1 or 2, which is fixed. The first optically anisotropic layer comprises at least one copolymer (polymer A) comprising a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1). The optical compensation film according to any one of claims 1 to 3, comprising:
General formula (1)

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent; L is selected from a divalent linking group selected from the following linking group group or the following linking group group. Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q is 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, or a hydrophilic group (—OH). Represents. The optical compensation film according to claim 1, wherein the first optically anisotropic layer contains at least one onium salt. A polarizing plate comprising the optical compensation film according to claim 1 and a polarizing film. The polarizing plate according to claim 6, wherein only a substantially isotropic adhesive layer and / or a substantially isotropic protective film is included between the optical compensation film and the polarizing film. The polarizing plate according to claim 7, wherein the transparent protective film is a film containing cellulose acylate, an in-plane retardation is 0 to 10 nm, and a retardation in the thickness direction is −20 to 20 nm. The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and the direction of the slow axis of the second optical anisotropic layer The polarizing plate according to claim 6, wherein the direction of the absorption axis of the polarizing film is substantially perpendicular to the polarizing film. The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and the slow axis of the second optical anisotropic layer The polarizing plate according to claim 6, wherein the direction and the direction of the absorption axis of the polarizing film are substantially parallel. A liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate according to claim 9, The first optically anisotropic layer, the second optically anisotropic layer, and the polarizing film are arranged in this order on the outside of one of the pair of substrates, and the second optically anisotropic layer is delayed. The polarizing plate is disposed so that the phase axis and the major axis direction of the liquid crystal molecules during black display are substantially parallel, and a second polarizing film is further provided outside the other substrate. A liquid crystal display device in which the absorption axes of the polarizing films are orthogonal to each other. A liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate according to claim 10, The first optically anisotropic layer, the second optically anisotropic layer, and the polarizing film are arranged in this order on the outer side of one of the pair of substrates, and the slow phase of the second optically anisotropic layer is in this order. The polarizing plate is arranged so that the axis and the major axis direction of the liquid crystal molecules at the time of black display are substantially orthogonal, and a second polarizing film is further provided on the outside of the other substrate, and both polarizing films Liquid crystal display device in which the absorption axes of each other are orthogonal to each other. 13. The only polarizing layer and / or the substantially isotropic transparent protective film only between the second polarizing film and the substrate is included. Liquid crystal display device. The transparent protective film is a film containing cellulose acylate, the in-plane retardation is 0 to 10 nm, the retardation in the thickness direction is -20 to 20 nm, and the haze of the transparent protective film is 1.0% or less. The liquid crystal display device according to claim 13.