JP2007206207A - Optical film, polarizing plate and liquid crystal display device - Google Patents

Abstract

【選択図】なしAn optical film capable of optically compensating an alignment layer without performing an alignment treatment and having good adhesion is provided. Moreover, the optical film which can be reduced in cost by reducing the number of processes is provided.
An alignment film placed on a hydrophilic surface of a transparent support contains a monomer or oligomer having a plurality of ethylenically unsaturated bonds in the molecule and a hydrophilic polymer, and is placed on the alignment film. An optical film in which the optically anisotropic layer contains a pyridinium compound represented by the general formula (I). (L ¹ is a divalent linking group, R ¹ is a hydrogen atom, an unsubstituted or substituted amino group, Y ¹ is a divalent linking group having a 5-membered or 6-membered ring as a partial structure, and Z is a halogen atom. A phenyl group substituted with an alkyl group, an alkyl group, an alkynyl group, an alkoxy group, etc. X is an anion.)
[Chemical 1]

[Selection figure] None

Description

  The present invention relates to a technical field of an optical film, a polarizing plate, and a liquid crystal display device, and more particularly to an optical film suitable for a liquid crystal display device such as an IPS mode, and a polarizing plate and a liquid crystal display device using the optical film.

  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 crystal 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 the increase / decrease in retardation of the liquid crystal layer during tilting, a white display or a halftone display is diagonally arranged between the substrate and the polarizing plate. It is disclosed that coloring can be improved when viewing directly from (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 positive birefringence and an optical axis in the normal direction of the film (see Patent Document 5), biaxial optical compensation sheet having a retardation of half wavelength 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) Has been.
Further, as means for producing an optical compensation material, methods described in Patent Documents 8 to 14 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 JP 2004-264345 A JP 2004-347698 A JP 2005-62425 A JP 2005-242322 A JP-A-2005-274909 JP 2005-173410 A JP-A-2005-258046

  However, when optically compensating an IPS mode or FFS mode liquid crystal cell using an optical compensation sheet made of a stretched birefringent polymer film, it is necessary to use a plurality of films, and as a result, the thickness of the optical compensation sheet increases. This is disadvantageous for thinning the display device. In order to solve these problems, an optically anisotropic film in which a liquid crystal material is aligned can be used, but it is difficult to apply the liquid crystal material in a large area with a uniform film thickness and align it uniformly. In addition, unevenness and surface irregularities are likely to occur, leading to a decrease in yield. Also, if the orientation of the liquid crystal material is insufficient, when used in a liquid crystal display device, the incident polarized light that has passed through the polarizing plate is depolarized and easily escapes to the front, causing light leakage during black display and reducing contrast. Etc. had occurred.

  Moreover, it was a problem to solve a decrease in the yield of the optical film due to an increase in the number of steps such as rubbing treatment, which is widely used when producing an optical film.

  That is, the present invention has been made in view of the above-described problems, and provides an optical film capable of optical compensation without performing an alignment treatment on the alignment layer. Another object of the present invention is to provide an optical film capable of reducing the cost by reducing the number of steps.

Means for solving the above-mentioned problems are as follows.
(1)
In an optical film comprising a transparent support having at least one surface made hydrophilic, an alignment film placed on the hydrophilic surface of the transparent support, and an optically anisotropic layer placed on the alignment film The alignment film contains a monomer or oligomer having a plurality of ethylenically unsaturated bonds in the molecule and a hydrophilic polymer, and the optically anisotropic layer contains a pyridinium compound represented by the following general formula (I): A featured optical film.

(In the formula (I), L ¹ represents a divalent linking group, an alkylene group and —O—, —S—, —CO—, —SO ₂ —, —NR ^a — (wherein R ^a represents a carbon atom) And a divalent linking group having 1 to 20 carbon atoms in combination with an alkenylene group, an alkynylene group or an arylene group, and R ¹ is a hydrogen atom. , An unsubstituted amino group or a substituted amino group substituted with a substituent having 1 to 20 carbon atoms, Y ¹ is a divalent having 1 to 30 carbon atoms having a 5-membered or 6-membered ring as a partial structure. Z is a halogen-substituted phenyl group, a nitro-substituted phenyl group, a cyano-substituted phenyl group, a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, or an alkoxy having 2 to 10 carbon atoms. A phenyl group substituted with a group, A kill group, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an aryloxycarbonyl group having 7 to 26 carbon atoms, (It is an arylcarbonyloxy group having 7 to 26 carbon atoms, and X is an anion.)
(2)
The optical film according to (1), wherein the hydrophilic polymer is a water-soluble etherified polysaccharide or polyvinyl alcohol.
(3)
When the surface of the transparent support on the alignment film side is measured by ESCA, the peak ratio of 290 eV and 288 eV on the carbon chart is 0.20 to 0.50 (1) or (2) The optical film described in 1.
(4)
The optical film according to any one of (1) to (3), wherein the optically anisotropic layer is composed of an oriented liquid crystalline layer containing a rod-like liquid crystalline compound.
(5)
The optically anisotropic layer includes a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. (1) to (4), comprising a fluoroaliphatic group-containing polymer containing one or more hydrophilic groups selected from the group, or a fluorine-containing compound represented by the following general formula (III) The optical film in any one of.
Formula (III)
(R ⁰ ) _mo −L ⁰ − (W) _no
(In the formula (III), R ⁰ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, and mo represents an integer of 1 or more. ⁰ may be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, L ⁰ represents a (mo + no) -valent linking group, and W represents a carboxyl group ( -COOH) or a salt thereof, a sulfo group (-SO ₃ H) or represents a salt thereof, or a phosphonoxy group {-OP (= O) (OH ) 2} or its salt, no represents an integer of 1 or more.)
(6)
The optical properties of the optically anisotropic layer are characterized in that the in-plane retardation Re is 0 to 10 nm and the retardation Rth in the thickness direction is −400 to −80 nm (1) to (5 ).
(7)
The optical film according to any one of (1) to (6), wherein the transparent support is made of a cellulose polymer.
(8)
The optical film according to (7), wherein the cellulose polymer contains at least one of cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose ether acetate.
(9)
Any of (1) to (8), wherein the optical characteristics of the transparent support are such that the in-plane retardation Re is 20 to 150 nm and the retardation Rth in the thickness direction is 100 to 300 nm. The optical film described in 1.
(10)
The optical film according to any one of (1) to (9), wherein the hydrophilization treatment of the transparent support is an alkali saponification treatment.
(11)
The alignment film according to any one of (1) to (10), wherein the alignment film is not rubbed.
(12)
A polarizing plate comprising the optical film according to any one of (1) to (11) and a polarizer.
(13)
A liquid crystal display device comprising the polarizing plate according to claim 12.
(14)
The liquid crystal display device according to (13), wherein the driving mode is an IPS format.

  According to the present invention, it is possible to perform optical compensation without performing an alignment treatment on the alignment layer, and an optical film having good adhesion can be obtained. In addition, the optical film of the present invention does not require a process such as an alignment process, and can reduce costs.

  Hereinafter, embodiments of the optical 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 this specification, “parallel” and “orthogonal” with respect to the axis mean that the angle is within a range of a strict angle of less than ± 10 °. In this range, an error from a strict angle is preferably less than ± 5 °, and more preferably less than ± 2 °. In addition, “substantially vertical” and “substantially parallel” for the liquid crystal molecules mean that they are 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 ± 10 °, and more preferably less than ± 5 °. Further, the “slow axis” means a direction in which the refractive index is maximized. Further, the measurement wavelength of the refractive index is a value at λ = 550 nm in the visible light region unless otherwise specified.

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

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

[Optically anisotropic layer]
The in-plane retardation Re of the optically anisotropic layer contained in the optical film of the present invention is preferably 0 to 10 nm, more preferably 0 to 5 nm, and most preferably 0 to 3 nm. . 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 −320 to −120 nm. Most preferred.

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

  The type of liquid crystal compound is not particularly limited. The optically anisotropic layer contained in the optical film of the present invention may be prepared, for example, by forming a low-molecular liquid crystalline 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 optically anisotropic layer contained in the optical film of the present invention, the molecules of the liquid crystalline 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 between the film surface 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.

  The optical film of the present invention can be incorporated into a polarizing plate, a liquid crystal display device or the like as an optical compensation film.

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

[Bar-shaped liquid crystalline compound]
In the present invention, it is preferable to form an 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. Nos. 4,683,327, 5,622,648, and 5,770,107, International Publication No. 95/22586. Pamphlet, pamphlet of 95/24455, pamphlet of 97/00600, pamphlet of 98/23580, pamphlet of 98/52905, JP-A-1-272551, JP-A-6-16616, 7-110469 JP, 11-80081, JP 2001-328773, JP 2004-240188, JP 2005-99236, JP 2005-99237, JP 2005-121827, Kai 2002-30042 Can be used compounds described like distribution.

[Vertical alignment control of liquid crystalline compounds]
In order to uniformly align the liquid crystalline compound vertically, it is necessary to vertically control the alignment of the liquid crystalline compound on the alignment film interface side and the air interface side. For this purpose, in the present invention, a liquid crystalline compound is vertically aligned by an excluded volume effect, electrostatic effect or surface energy effect with respect to an alignment film containing a monomer or oligomer having a plurality of ethylenically unsaturated bonds in the molecule. A liquid crystal composition to which a compound having an effect of aligning is added is employed. In addition, with regard to alignment control on the air interface side, a compound that is unevenly distributed at the air interface during alignment of the liquid crystalline compound and acts to align the liquid crystalline compound vertically by its excluded volume effect, electrostatic effect, or surface energy effect is blended The liquid crystal composition may be used. In the present invention, a pyridinium derivative is used as a compound (alignment film side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystalline compound on the alignment film interface side. As a compound (air interface side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystal compound on the air interface side, a fluoro aliphatic group that promotes the uneven distribution of the compound on the air interface side, One or more hydrophilic groups selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof A compound is preferably used. Further, by blending these compounds, for example, when a liquid crystalline composition is prepared as a coating solution, the coating property of the coating solution is improved, and the occurrence of unevenness and repellency is suppressed. The vertical alignment agent will be described in detail below.

[Alignment film side vertical alignment agent] (pyridinium compound)
In the present invention, a pyridinium derivative (pyridinium salt) represented by the following formula (I) is used as the alignment film side vertical alignment agent. By adding at least one of the pyridinium derivatives to the liquid crystal composition, the molecules of the rod-like liquid crystal compound can be aligned substantially vertically in the vicinity of the alignment film. When the alignment film contains a hydrophilic polymer and the alignment film surface is hydrophilic, the pyridinium compound is considered to be unevenly distributed on the alignment film side from the hydrophobic air interface side. The liquid crystal can be aligned without rubbing the surface of a certain alignment film.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The preferable range of the content of the pyridinium derivative in the liquid crystal composition varies depending on the use, but 0.005 in the liquid crystal composition (liquid crystal composition excluding the solvent when prepared as a coating liquid). It is preferably -8% by mass, more preferably 0.01-5% by mass.

[Air interface side vertical alignment agent]
Examples of the air interface side vertical alignment agent include a fluoro aliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. A fluoroaliphatic group-containing polymer (hereinafter referred to as “fluorine polymer”) containing one or more hydrophilic groups selected from the group consisting of the above, or a fluorine-containing compound represented by the general formula (III) is preferably used. It is done.

(Air interface side vertical alignment agent (1): Fluoropolymer)
First, the fluorine polymer will be described.
The fluoropolymer is selected from the group consisting of a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. Containing at least one kind of hydrophilic group. The types of polymers are described in “Revised Chemistry of Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku Dojin Co., 1968) on pages 1 to 4, for example, polyolefins, polyesters, polyamides, polyimides. , Polyurethanes, polycarbonates, polysulfones, polycarbonates, polyethers, polyacetals, polyketones, polyphenylene oxides, polyphenylene sulfides, polyarylates, polytetrafluoroethylene (PTFE), polyvinylidene fluorides And cellulose derivatives. The fluoropolymer is preferably a polyolefin.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Formula (III) -b
(R ⁶ -L ^2- ) _m2 (Ar ¹ ) -W ³
In formula (III) -b, R ⁶ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, m2 represents an integer of 1 or more, R ⁶ may be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal. L ² represents an alkylene group, an aromatic group, —CO—, —NR′— (R ′ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, It represents a divalent linking group selected from the group consisting of —SO ₂ — and combinations thereof, and a plurality of L ² may be the same or different. Ar ¹ represents an aromatic hydrocarbon ring or an aromatic heterocycle, W ³ represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group or an alkylamino group having a carboxyl group, a sulfo group or a phosphonoxy group as a substituent.

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

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

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

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

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

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

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

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

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

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

  The preferable range of the content of the fluorine-containing compound in the liquid crystal composition varies depending on the use, but 0.005 to 0.005 in the liquid crystal composition (a composition excluding the solvent in the case of a coating liquid). The content is preferably 8% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.05 to 1% by mass.

[Polymerization initiator]
It is preferable to fix the molecules of the liquid crystal compound aligned in a desired alignment state (for example, vertical alignment in the case of a rod-like liquid crystal compound) while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction of the polymerizable group (P) introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970).
It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is more preferable that it is 0.5-5 mass%.

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

  Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the polymerizable group-containing liquid crystalline compound. Examples thereof include those described in JP-A-2002-296423, paragraph numbers [0018] to [0020]. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraph numbers [0028] to [0056] of JP-A No. 2001-330725 and compounds described in paragraph numbers [0069] to [0126] of JP-A No. 2005-62673 can be 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 JP-A 2000-155216, paragraph [0178]. 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.

[Application]
The optically anisotropic layer of the present invention supports, for example, a coating solution prepared by dissolving and / or dispersing an additive such as a liquid crystalline compound, an alignment control agent, and a polymerization initiator that is optionally added in a solvent. It can be formed by applying on the body. As the solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

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

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

[Transparent support]
As a support for forming an optically anisotropic layer made of a liquid crystalline compound, it is preferable to use a support having optical properties described later. The support preferably has a light transmittance of 80% or more.

The support (transparent substrate) may be optically isotropic, but depending on the function required for the liquid crystal display device on which the retardation plate is mounted, the transparent substrate has optical anisotropy. It is preferable to have. The optical anisotropy in this case is not particularly limited. For example, optical anisotropy exhibiting a so-called positive or negative A-Plate phase difference characteristic, or optical anisotropy exhibiting a positive or negative C-Plate phase difference characteristic. , Optical anisotropy exhibiting positive or negative O-Plate phase difference characteristics, biaxial optical anisotropy having refractive index anisotropy in different directions (that is, having two optical axes), etc. It is. Note that A-plate, C-plate, and O-plate all refer to layers having so-called uniaxial optical anisotropy.
The A-plate has a positive (positive) A-plate when the optical axis is in the in-plane direction and the optical characteristic condition satisfies the following formula (I), and negative when the optical characteristic condition satisfies the following formula (B). It is called (negative) A-plate.

nx> ny≈nz (I)
ny <nx≈nz (ro)

  The C-plate has a positive (positive) C-plate when the optical axis exists in the Z-axis direction, that is, in the thickness direction, and the optical characteristic condition satisfies the following formula (ha). When the condition is satisfied, it is called a negative (negative) C-plate.

nx≈ny <nz (ha)
nx≈ny> nz (to)

  In the present invention, nx, ny, and nz indicate refractive indexes in the X-axis, Y-axis, and Z-axis directions in the layer having optical anisotropy. However, the X-axis direction is a direction (in-plane slow axis direction) in which the refractive index is maximum in the plane of the optically anisotropic layer, and the Y-axis direction is the optically anisotropic layer. Is the direction perpendicular to the X-axis direction (in-plane fast axis direction), and the Z-axis direction is the thickness of the optically anisotropic layer perpendicular to the X-axis direction and the Y-axis direction. Direction.

  In the O-plate, the optical axis direction is inclined as viewed from the in-plane direction and the Z-axis direction (thickness direction perpendicular to the in-plane direction). The means for imparting optical anisotropy is not particularly limited, and a known method may be applied as appropriate.For example, the optical anisotropy transparent film is imparted with optical anisotropy by stretching, etc. It can be set as a support body (transparent base material).

  The in-plane retardation Re of the transparent support is preferably 20 to 150 nm, more preferably 30 to 130 nm, and most 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 most preferably 140 nm to 260 nm.

Examples of the polymer include cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate and cyclic polyolefin. Cellulose esters are preferred, acetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and cellulose ether acetate are more preferred, and triacetyl cellulose is most preferred.
The method for producing a support using cellulose acetate propionate and cellulose acetate butyrate is the method described in JP-A-2005-165650, and the method for producing a support using cellulose ether acetate is a method described in JP-A-2005-283997. Is preferably used.
As the cyclic polyolefin, a polymer obtained by hydrogenation reaction of a ring-opening polymer of tetracyclododecene or a ring-opening copolymer of tetracyclododecene and norbornene described in JP-B-2-9619 Can be used from the series of Arton (manufactured by JSR), Zeonex, and Zeonore (manufactured by Nippon Zeon).

The polymer film is preferably formed by a solvent cast method. The thickness of the transparent support is preferably 20 to 500 μm, and more preferably 50 to 200 μm.
The surface of the transparent support is preferably hydrophilized so that the pyridinium compound (alignment film side vertical alignment agent) represented by the general formula (I) can move to the support side. In order to hydrophilize the surface of the transparent support, it is preferable to perform surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment) on the transparent support. It is more preferable to saponify.
For the saponification treatment, it is preferable to use a method described in JP-A No. 2003-313326, JP-A No. 2004-354962, JP-A No. 2005-62799, JP-A No. 2005-115341, or the like.

  The surface of the support after the hydrophilization treatment preferably has an A value (peak ratio of 290 eV and 288 eV on the carbon chart measured by ESCA) measured by the following method of 0.20 to 0.50. 0.20 to 0.45 is more preferable, and 0.20 to 0.32 is still more preferable. When the A value is larger than 0.50, the “alignment film side vertical alignment agent” does not sufficiently move to the hydrophilic surface side, and the optically anisotropic layer may not obtain desired optical characteristics.

  Nine-point sampling is performed on the polymer film in the width direction, and the carbon atom spectrum on the surface of the saponified film is measured using a photoelectron spectrometer (“ESCA750” type, manufactured by Shimadzu Corporation). When the binding energy (eV) is plotted on the X axis and the intensity (CPS) is plotted on the Y axis, the peak near 288 eV is derived from the C—O bond, and the peak at 290 eV is derived from the C═O bond. It is a peak. The C = O and C-O peaks may move on the X axis depending on the measurement environment. However, since the peak itself disappears on the surface that has been sufficiently hydrophilized, the C = O peak does not move on the X-axis for convenience in such a case, and at 290 eV (signal-base) The difference is C = O intensity, and A = [peak C = O] / [peak C—O], that is, the peak ratio of 290 eV and 288 eV on the carbon chart is calculated.

  The average particle size is about 10 to 100 nm for the transparent support or the long transparent support in order to give slippage in the transport process or to prevent the back surface and the surface from sticking after winding. It is preferable to use what formed the polymer layer which mixed inorganic particle 5%-40% by solid content mass ratio on the one side of the support body by application | coating or co-casting with a support body.

[Alignment film]
In the present invention, an alignment film containing a monomer or oligomer having a plurality of ethylenically unsaturated bonds in the molecule and a hydrophilic polymer is formed on the hydrophilic surface of the transparent support.

(Monomer or oligomer contained in alignment film)
The monomer or oligomer contained in the alignment film is used for imparting adhesion between the alignment film, the optically anisotropic layer, and the support. The monomer or oligomer used in the present invention is preferably one that does not interfere with the effect of the alignment film side vertical alignment agent.

  Specific examples of monomers and oligomers containing a plurality of ethylenically unsaturated bonds in the molecule include, for example, polyethylene glycol di (meth) acrylate and ethylene oxide described in paragraph [0044] of JP-A-2004-206102. Modified bisphenol A di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, di- or polyepoxy compounds An epoxy (meth) acrylate to which (meth) acrylic acid is added can be mentioned.

(Hydrophilic polymer contained in alignment film)
As the polymer contained in the alignment film, it is preferable to use a hydrophilic polymer capable of obtaining the effect of the alignment film side vertical alignment agent. Specifically, for example, a water-soluble polysaccharide described in paragraph [0025] of JP-A-2004-206102 [water-soluble cellulose (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxy Methylcellulose sodium salt, carboxymethylcellulose ammonium salt, etc.), starch, hydroxypropyl starch, carboxymethyl starch, pullulan, chitosan, cyclodextrin], polyvinyl alcohol having a saponification degree of 80% or more, gelatin, ovalbumin, candy and straw And DNA obtained from calf thymus.
Water-soluble etherified polysaccharides (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl starch, etc.) or polyvinyl alcohol are preferred.

(Photopolymerization initiator used for curing the alignment film)
The alignment film used in the present invention is preferably hardened before applying the liquid crystal composition by ultraviolet rays, electron beams, thermal polymerization or the like. When the liquid crystal composition is coated and hardened, the alignment film may be hardened simultaneously. When the liquid crystal composition is applied, the monomer or oligomer present in the alignment film may be extracted from the alignment film by the solvent of the liquid crystal composition, so the alignment film is hardened before applying the liquid crystal composition. It is preferable to form a film. In order to harden the alignment film, it is preferable to polymerize by adding a photopolymerization initiator to the alignment film. Specifically, compounds described in JP-A-2004-206102 [0046] [Irgacure 651, Irgacure 184, Irgacure 2959, Irgacure 1800, Irgacure 1850 (trade name, manufactured by Ciba Specialty Chemicals)] and WS triazine (Three (Manufactured by Wa Chemical).

  For the formation of the alignment film, a bar coating method and a die coating method are preferably used, 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.

  In the optical film of the present invention, as described above, an optically anisotropic layer containing an “alignment film side vertical alignment agent” (further, an “air interface side vertical alignment agent”) is placed on a hydrophilic support surface. Since the liquid crystalline compound of the optically anisotropic layer is aligned by being present on the alignment film, it is not always necessary to rub the surface of the alignment film on the optically anisotropic layer side, and for aligning the liquid crystalline layer There is no need to contact (bond) the treated support to the liquid crystalline layer. Therefore, since the optical film of the present invention does not include a rubbing process or a contact (bonding) process, there is a possibility that it can be produced at a low cost and defects due to the process can be reduced.

[Polarizer]
The polarizing plate of the present invention includes an optical film having the optically anisotropic layer of the present invention (sometimes referred to as “optical compensation film”) 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.

  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. In the present invention, when the optically anisotropic layer is formed on a transparent support, the transparent support can function as a protective film. When a protective film of a polarizing film is used separately from the support, it is preferable to use a cellulose ester film having high optical isotropy as the protective film.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes at least the optical film of the present invention. The optical film may be incorporated into the liquid crystal display device as a single member. Moreover, you may incorporate in the liquid crystal display device as an optically anisotropic layer of an optical compensation film, a constituent layer of a polarizing plate, or the like. 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 optical film of this invention. The use position of the optical film of the present invention is not particularly limited, and may be one or more. The liquid crystal cell is not particularly limited, and a general liquid crystal cell such as a liquid crystal layer sandwiched between a pair of transparent substrates provided with electrodes can be used. The transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction. Specifically, a transparent substrate in which the substrate itself has a property of orienting liquid crystals, a transparent substrate in which an alignment film having the property of orienting liquid crystals is provided, but the substrate itself lacks the alignment ability. Either can be used. Moreover, a well-known thing can be used for the electrode of a liquid crystal cell. Usually, it can be provided on the surface of the transparent substrate in contact with the liquid crystal layer, and when a substrate having an alignment film is used, it can be provided between the substrate and the alignment film. The material exhibiting liquid crystallinity for forming the liquid crystal layer is not particularly limited, and examples thereof include various ordinary low-molecular liquid crystalline compounds, high-molecular liquid crystalline compounds, and mixtures thereof that can constitute various liquid crystal cells. Moreover, a pigment | dye, a chiral agent, a non-liquid crystalline compound, etc. can also be added to these in the range which does not impair liquid crystallinity.

  In addition to the electrode substrate and the liquid crystal layer, the liquid crystal cell may include various components necessary for forming various types of liquid crystal cells described later. As the liquid crystal cell system, 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 disposed between the reflecting plate and the polarizing film (between the reflecting plate and the liquid crystal cell or between the liquid crystal cell and the polarizing film). The reflector may share the liquid crystal cell and the substrate. The transflective liquid crystal display device includes a liquid crystal cell, a polarizing plate disposed closer to the viewer than the liquid crystal cell, at least one retardation plate disposed between the polarizing plate and the liquid crystal cell, At least a transflective layer disposed behind the liquid crystal cell as viewed from the observer, and at least one retardation plate and a polarizing plate behind the transflective layer as viewed from the observer Yes. In this type of liquid crystal display device, it is possible to use both a reflection mode and a transmission mode by installing a backlight.

  In an IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. In the IPS mode, black is displayed when no electric field is applied, and the transmission axes of the pair of upper and lower polarizing plates are orthogonal. JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light at the time of black display in an oblique direction and improving a viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.

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

[Example 1] (Film formation of cellulose acetate film)
(1) Cellulose acetate Cellulose acetate having a substitution degree of 2.81 was prepared according to the description of paragraphs [0081] and [0090] to [0091] of JP-A-2002-338601.

(2) Dissolution With respect to 100 parts by mass of the cellulose acetate, a plasticizer (TPP: triphenyl phosphate 7.8 parts by mass, BDP: biphenyl diphenyl phosphate 3.9 parts by mass), the following retardation developer (1) 6.4 Part by mass was added to a mixed solvent dichloromethane / methanol (87/13 parts by mass) with stirring so that the mass concentration of cotton was 15% by mass, and heated to stir to dissolve. At the same time, 0.05 part by mass of a matting agent (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) and 0.0009 part by mass of the following dye (1) are added to 100 parts by mass of cellulose acetate and heated. While stirring.

(3) Casting The above-mentioned dope was cast using a band casting machine. A film having a residual solvent amount of 25 to 35% by mass and peeled off from the band is 3% in the interval from stripping to tenter under the condition that the stretching temperature is in the range of about Tg-5 to Tg + 5 ° C. (Tg: 142 ° C.). The film was stretched in the longitudinal direction at a stretching ratio of, then stretched in the width direction at a stretching ratio of 32% using a tenter, and immediately after transverse stretching, the film was shrunk in the width direction at a ratio of 0 to 10%, and then the film was detached from the tenter. Then, a cellulose acetate film CF-1 was formed. Both ends were cut off in front of the winding part to make a width of 2000 mm and wound up as a roll film having a length of 4000 m. With respect to the produced cellulose acetate film CF-1, the Re retardation value and the Rth retardation value at a wavelength of 590 nm were measured at 25 ° C. and 60% RH, and were found to be 55 nm and 200 nm, respectively. Rth _(λ) was calculated with the average refractive index of the film being 1.48.

(Preparation of saponification film KF-1)
The cellulose acetate film CF-1 produced above was passed through a dielectric heating roll heated to 60 ° C., heated to 40 ° C., and then the following alkali saponification solution kept at 40 ° C. was added to a 17 mL / m using a rod coater. ² applied. After holding for 7 seconds under a steam far infrared heater manufactured by Noritake Company Limited, heated to 110 ° C, 1.4 mL / m ^{2 of} pure water was applied using the same rod coater, and the alkali was washed off. It was. At this time, the film temperature was maintained at 40 to 45 ° C., and the KOH concentration of the coating film after application of pure water was 0.6 normal. Next, washing with a fountain coater and draining with an air knife were repeated four times, and after washing off the alkali, it was retained in a drying zone at 70 ° C. for 5 seconds and dried to produce a saponified film KF-1. The value of C═O / C—O measured by ESCA on the saponified film surface was 0.20.

――――――――――――――――――――――――――――――――――
Alkaline saponification solution composition ――――――――――――――――――――――――――――――――――
Potassium hydroxide 4.7 parts by weight Water 15.7 parts by weight Isopropanol 64.8 parts by weight Propylene glycol 14.9 parts by weight C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) ₁₀ H (surfactant) 1.0 mass Department ――――――――――――――――――――――――――――――――――

  Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), the optical properties of the produced saponified film KF-1 were measured. Re measured at a wavelength of 590 nm was 55 nm, and Rth was 200 nm.

(Addition of alignment film)
On the surface of the saponified film KF-1 produced above, the following alignment film coating solution A was continuously applied at the coating speed of 20 m / min under the following conditions, and the transparent support provided with the alignment film was supported with a width of 1340 mm. 500 m was obtained.
・ Apply 24 mL / m ² and dry at 100 ° C. for 2 minutes.
・ Air-cool at room temperature.
-Irradiate 600 mJ of ultraviolet rays (maximum wavelength: 370 to 390 nm).

(Example of alignment film)
―――――――――――――――――――――――――――――――――――――
Alignment film coating solution A composition ―――――――――――――――――――――――――――――――――――――
Hydroxyethyl cellulose (HEC Daicel SP200, manufactured by Daicel Chemical Industries) 2.0 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (SR-9035, manufactured by Nippon Kayaku Co., Ltd.) 0.1 parts by mass polymerization initiator (Irgacure 2959, Ciba Specialty) Chemicals) 0.01 parts water 72.0 parts methanol 8.0 parts ―――――――――――――――――――――――――――――― ―――――――

  The coating liquid S1 containing a rod-like liquid crystalline compound having the following composition was continuously applied onto the alignment film produced above 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 60 ° C., the orientation of the liquid crystal compound was fixed by UV irradiation, and an optically anisotropic layer was formed. Subsequently, as a water immersion treatment for polarizing plate processing, which will be described later, a 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 add sodium hydroxide. Washed away. 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, the optical compensation film of Example 1 on which the optically anisotropic layer was laminated was produced.

――――――――――――――――――――――――――――――――――
Composition of coating liquid (S1) containing rod-like liquid crystalline compound ――――――――――――――――――――――――――――――――――
The following rod-like liquid crystalline compound (I) 100 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Polymer 0.4 parts by weight The following pyridinium salt 1 part by weight Methyl ethyl ketone 172 parts by weight ――――――――――――――――――――――――――――――――― -

[Examples 2 to 5]
Example 1 except that a coating liquid containing a hydrophilic polymer, a monomer, a polymerization initiator, water, and methanol in the composition shown in Table 1 was prepared instead of the alignment film coating liquid A as an alignment film, and the coating liquid was dried. Thus, optical compensation films of Examples 2 to 5 were produced.

[Comparative Example 1]
In place of the alignment film coating solution A, a coating solution containing 2.0 parts by mass of the polymer, 72.0 parts by mass of water and 8.0 parts by mass of methanol described in Example 1 of JP-A-9-152509 is prepared. The optical compensation films of Examples 2 to 5 were prepared by the method of Example 1 except that the coating and drying were performed.

[Comparative Examples 2 to 4]
An optical film of Comparative Example 2 was obtained in the same manner as in Example 1 except that the monomer and the polymerization initiator were removed from the alignment film coating solution A of Example 1. In addition, when the transparent support of Example 1 was not saponified and the temperature at which the transparent support was saponified was kept at 25 ° C., coating was performed in the same manner as in Example 1 to obtain optical films of Comparative Examples 3 and 4.

(Evaluation)
<Orientation>
The orientation of the liquid crystal layer was confirmed by placing an optical film between two polarizing plates arranged in crossed Nicols. It was found that the vertically aligned sample was dark when placed parallel to the plane of the polarizing plate and slightly brightened when tilted with respect to the plane of the polarizing plate. When the non-oriented sample was placed between the polarizing plates, the light was irregularly reflected and clouded.
<Adherence>
Adhesion of the liquid crystalline layer was confirmed by applying and peeling an adhesive tape (No31HR, manufactured by Nitto Denko Corporation) on a 25 mm square on the liquid crystalline layer. It can be seen that those with close contact are not peeled off when the sample is placed between polarizing plates arranged in crossed Nicol after the tape is peeled off. It can be seen that those that do not adhere are peeled off.
The said evaluation result about the optical film of Examples 1-7 and Comparative Examples 1-3 was put together in Table 1 with the other item, and was shown.

  In the optical films of Examples 1 to 5, the liquid crystalline layer was vertically aligned and had adhesiveness. On the other hand, the optical films of Comparative Examples 1 to 4 did not have adhesiveness.

[Comparative Example 5]
Instead of the alignment film coating solution A, a coating solution obtained by removing hydroxyethyl cellulose from the coating solution A was prepared and applied. The coating liquid (S1) containing the rod-shaped liquid crystal compound of Example 1 was applied thereto to produce an optical film of Comparative Example 5. This liquid crystalline layer was not vertically aligned.

[Comparative Example 6]
An optical film of Comparative Example 6 was produced in the same manner as in Example 1 except that the coating liquid (S2) obtained by removing the pyridinium salt from the coating liquid (S1) containing the rod-like liquid crystal compound was used. This liquid crystalline layer was not vertically aligned.

[Comparative Example 7]
The alignment solution of Example 1 was coated in the same manner as in Example 1 except that the monofunctional monomer hydroxyethyl acrylate (produced by Osaka Organic Chemical Industry Co., Ltd.) was added instead of ethylene oxide-modified trimethylolpropane triacrylate. The optical film of Example 7 was obtained. This optical film had no adhesion.

[Comparative Example 8]
An optical film of Comparative Example 8 was obtained in the same manner as in Example 1 except that the transparent support coated with the alignment film of Example 1 was not irradiated with ultraviolet light. This optical film had insufficient adhesion.

[Reference Example] (with rubbing treatment)
The alignment film surface of the transparent support coated with the alignment film prepared in Example 1 is conveyed with one rubbing roll, a peripheral speed of 200 m / min (rubbing cloth YA-19-RE, manufactured by Yoshikawa Chemical Co., Ltd.), The film was rubbed at a speed of 20 m / min, and the coating liquid (S1) of Example 1 was continuously applied, aged and cured to obtain a film having a coating width of 1300 mm and a coating length of 500 m.
When this film was inspected for light leakage defects under crossed Nicols conditions, defects were observed at a rate of 6 m / piece. When the film of Example 1 was inspected under the same conditions, defects were observed at a rate of 80 m / piece. As described above, it can be seen that the film according to the present invention without the rubbing treatment is improved in productivity.

[Example 8] (using cellulose ether acetate film)
For 100 parts by mass of cellulose ether acetate described in Synthesis Example 1 of JP-A-2005-283997, a plasticizer (TPP: triphenyl phosphate 7.8 parts by mass, BDP: biphenyl diphenyl phosphate 3.9 parts by mass), 6.4 parts by mass of the retardation developer (1) is added to a mixed solvent dichloromethane / methanol (87/13 parts by mass) while stirring so that the mass concentration of cotton becomes 15% by mass, and heated to stir to dissolve. It was. At this time, 0.05 parts by mass of a matting agent (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.), which is fine particles, and 0.0009 parts by mass of the dye (1) are added simultaneously (with respect to 100 parts by mass of cellulose ether acetate). And stirred while heating.

(Casting)
The above dope was cast using a band casting machine. A film having a residual solvent amount of 25 to 35% by weight and peeled off from the band is 3% in the interval from stripping to tenter under the condition that the stretching temperature is in the range of about Tg-5 to Tg + 5 ° C. (Tg: 134 ° C.). The film was stretched in the longitudinal direction at a stretching ratio of, then stretched in the width direction at a stretching ratio of 32% using a tenter, and immediately after transverse stretching, the film was shrunk in the width direction at a ratio of 0 to 10%, and then the film was detached from the tenter. Then, a cellulose ether acetate film CF-2 was formed. Both ends were cut off in front of the winding part to make a width of 2000 mm and wound up as a roll film having a length of 4000 m. With respect to the produced cellulose ether acetate film CF-2, Re retardation value and Rth retardation value at a wavelength of 590 nm at 25 ° C. and 60% RH were 55 nm and 200 nm. Rth _(λ) was calculated with the average refractive index of the film being 1.48.

On the transparent support of the cellulose ether acetate film CF-2 prepared above, the saponification treatment, adhesion layer application, and optical anisotropic layer application performed in Example 1 were performed to prepare the optical compensation film of Example 8. did. The produced film had no problem in orientation.
Note that the value of C═O / C—O measured by ESCA on the surface of the film obtained by saponifying the film CF-2 was 0.25.

[Example 9] (using cellulose acetate butyrate film)
1. Formation of Cellulose Acetate Butyrate Film (1) Cellulose Acetate Butyrate Cellulose acetate butyrate was prepared according to the method described in paragraph [0031] of JP-A-10-45803 as follows.
30 parts by mass of acetic acid and 313.8 parts by mass of butyric acid were added to 100 parts by mass of cellulose and mixed at 54 ° C. for 30 minutes. After the mixture was cooled, 15.5 parts by mass of acetic anhydride, 245.6 parts by mass of butyric anhydride and 3.5 parts by mass of sulfuric acid cooled to about −20 ° C. were added for esterification. The maximum temperature in esterification was adjusted to 40 ° C. After performing the esterification reaction for 180 minutes, a mixed solution of 95 parts by mass of acetic acid and 32 parts by mass of water was added as a reaction terminator over 20 minutes to hydrolyze excess anhydride. The temperature of the reaction solution was kept at 60 ° C., and 290 parts by mass of acetic acid and 100 parts by mass of water were added. After 1 hour, an aqueous solution containing 5.7 parts by mass of magnesium acetate was added to neutralize sulfuric acid in the system. The obtained cellulose acetate butyrate had an acetyl substitution degree of 0.2 and a butyryl substitution degree of 2.3 (total substitution degree of 2.5).

(2) Dope preparation (2) -1 Cellulose acetate butyrate solution The following cellulose acetate butyrate composition was put into a mixing tank, stirred to dissolve each component, and further heated to 90 ° C. for about 10 minutes. The solution was filtered through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm to obtain a cellulose acetate butyrate solution.

(Cellulose acetate butyrate solution composition)
Cellulose acetate butyrate 100.0 parts by mass Triphenyl phosphate 7.8 parts by mass Biphenyl diphenyl phosphate 3.9 parts by mass Methylene chloride 403.0 parts by mass Methanol 60.2 parts by mass

(2) -2 Matting Agent Dispersion Solution Next, the following matting agent dispersion composition containing the cellulose acylate solution prepared above was charged into a disperser to prepare a matting agent dispersion.

(Matting agent dispersion composition)
Silica particles having an average particle diameter of 16 nm {aerosil R972: manufactured by Nippon Aerosil Co., Ltd.} 2.0 parts by mass Methylene chloride 72.4 parts by mass Methanol 10.8 parts by mass Cellulose acylate solution 10.3 parts by mass

  100 parts by weight of the cellulose acetate butyrate solution, 1.35 parts by weight of the matting agent dispersion, and 5.8 parts of plasticizer (2/1 (parts by weight) mixture of TPP: triphenyl phosphate, BDP: biphenyl diphenyl phosphate). The dope for film formation was prepared by mixing so as to have a ratio of parts by mass.

(3) Casting Film Formation and Evaluation The film forming dope described above was cast using a band casting machine. A film peeled off from the band with a residual solvent amount of 25 to 35% by mass is stretched at a stretching ratio of 20% using a tenter under a condition where the stretching temperature is in the range of about Tg-5 to Tg + 5 ° C. (Tg: 120 ° C.). Was then stretched in the width direction to produce a cellulose acetate butyrate film CF-3 (film thickness after drying: 120 μm).
For the produced cellulose acetate butyrate film CF-3, the Re retardation value and the Rth retardation value at a wavelength of 590 nm were measured at 25 ° C. and 60% RH using KOBRA-21ADH (manufactured by Oji Scientific Instruments). However, they were 53 nm and 196 nm, respectively.

On the transparent support of the cellulose acetate butyrate film CF-3 produced above, the saponification treatment, adhesion layer application, and optical anisotropic layer application performed in Example 1 were performed to obtain the optical compensation film of Example 9. Produced. The produced film had no problem in orientation.
Note that the value of C═O / C—O measured by ESCA on the surface of the film obtained by saponifying the film CF-3 was 0.22.

[Example 10] (using cellulose acetate propionate film)
In the method described in paragraph numbers [0136] to [0163] of JP-A-2005-134608, the optical compensation film No. By adjusting the film thickness of 13 to 90 μm, a cellulose acetate propionate film CF-4 having Re of 53 nm and Rth of 198 nm at a wavelength of 590 nm was obtained.

On the transparent support of the cellulose acetate propionate film CF-4 produced above, the saponification treatment, adhesion layer application, and optical anisotropic layer application performed in Example 1 were performed, and the optical compensation film of Example 10 was performed. Was made. The produced film had no problem in orientation.
Note that the value of C═O / C—O measured by ESCA on the surface of the film obtained by saponifying the film CF-4 was 0.21.

<Preparation of polarizing plate>
A polarizing film is prepared by adsorbing iodine to a stretched polyvinyl alcohol film, and a commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is subjected to saponification treatment, and a polarizing plate using a polyvinyl alcohol adhesive Affixed to one side. Further, the films CF-1 to CF-4 produced in Example 1 and Examples 8 to 10 were similarly attached to the other side of the polarizing plate so that the liquid crystalline layer was on the opposite side of the polarizing film, Polarizing plate 1 and polarizing plates 8 to 10 were prepared.
Similarly, iodine is adsorbed to a stretched polyvinyl alcohol film to produce a polarizing film, and a commercially available cellulose acetate film (Fuji Tac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) is subjected to saponification treatment to obtain a polyvinyl alcohol adhesive. Attached on both sides of the polarizing plate to prepare a polarizing plate A.

<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 plate was bonded to the upper and lower glass substrates of the parallel alignment cell using an adhesive. At this time, the polarizing plates 1, 8 to 10 and A are disposed on the polarizing plate on the backlight side, the polarizing plate A is disposed on the viewer side, and the optical anisotropic layer included in the polarizing plates 1 and 8 to 10 is provided. The substrates were bonded so as to be in contact with the glass substrate on the backlight side. In addition, the absorption axis of the polarizing plate on the backlight side and the slow axis of the liquid crystal cell were orthogonal to each other, and the absorption axes of the upper and lower polarizing plates 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. In this way, liquid crystal display devices 1, 8 to 10 and A were produced.

(Measurement of leakage light of the manufactured liquid crystal display device)
The leakage light of the liquid crystal display device thus manufactured was measured. The measuring device (luminance meter BM-5, manufactured by Topcon Corporation) was used, and the ratio of the light source luminance to the leakage light luminance was defined as the transmittance. The liquid crystal display devices 1, 8 to 10 and A using the polarizing plate of the present invention were observed obliquely from 60 ° to the left. The results are shown in Table 2.

  As described above, it can be seen that the leakage light of the liquid crystal display devices 1 and 8 to 10 using the polarizing plates 1 and 8 to 10 of the present invention is better than the liquid crystal display device A of the comparative example.

Claims (14)

In an optical film comprising a transparent support having at least one surface made hydrophilic, an alignment film placed on the hydrophilic surface of the transparent support, and an optically anisotropic layer placed on the alignment film The alignment film is formed by curing a composition containing a monomer or oligomer having a plurality of ethylenically unsaturated bonds in the molecule and a hydrophilic polymer. The optically anisotropic layer has the following general formula (I): The optical film characterized by including the pyridinium compound represented by these.

(In the formula (I), L ¹ represents a divalent linking group, an alkylene group and —O—, —S—, —CO—, —SO ₂ —, —NR ^a — (wherein R ^a represents a carbon atom) And a divalent linking group having 1 to 20 carbon atoms in combination with an alkenylene group, an alkynylene group or an arylene group, and R ¹ is a hydrogen atom. , An unsubstituted amino group or a substituted amino group substituted with a substituent having 1 to 20 carbon atoms, Y ¹ is a divalent having 1 to 30 carbon atoms having a 5-membered or 6-membered ring as a partial structure. Z is a halogen-substituted phenyl group, a nitro-substituted phenyl group, a cyano-substituted phenyl group, a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, or an alkoxy having 2 to 10 carbon atoms. A phenyl group substituted with a group, A kill group, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an aryloxycarbonyl group having 7 to 26 carbon atoms, (It is an arylcarbonyloxy group having 7 to 26 carbon atoms, and X is an anion.)   The optical film according to claim 1, wherein the hydrophilic polymer is a water-soluble etherified polysaccharide or polyvinyl alcohol.   3. The peak ratio of 290 eV and 288 eV on the carbon chart is 0.20 to 0.50 on the carbon chart when the surface of the transparent support on the alignment film side is measured by ESCA. Optical film.   The optical film according to any one of claims 1 to 3, wherein the optically anisotropic layer comprises an oriented liquid crystalline layer containing a rod-like liquid crystalline compound. The optically anisotropic layer includes a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. 5. A fluoroaliphatic group-containing polymer containing one or more hydrophilic groups selected from the group, or a fluorine-containing compound represented by the following general formula (III): An optical film according to any one of the above.
Formula (III)
(R ⁰ ) _mo −L ⁰ − (W) _no
(In the formula (III), R ⁰ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, and mo represents an integer of 1 or more. ⁰ may be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal, L ⁰ represents a (mo + no) -valent linking group, and W represents a carboxyl group ( -COOH) or a salt thereof, a sulfo group (-SO ₃ H) or represents a salt thereof, or a phosphonoxy group {-OP (= O) (OH ) 2} or its salt, no represents an integer of 1 or more.)   The optical properties of the optically anisotropic layer are characterized in that in-plane retardation Re is 0 to 10 nm and thickness direction retardation Rth is -400 to -80 nm. The optical film in any one.   The optical film according to claim 1, wherein the transparent support is made of a cellulose polymer.   The optical film according to claim 7, wherein the cellulosic polymer includes at least one of cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and cellulose ether acetate.   The optical characteristics of the transparent support are as follows: in-plane retardation Re is 20 to 150 nm, and retardation Rth in the thickness direction is 100 to 300 nm. Optical film.   The optical film according to claim 1, wherein the hydrophilic treatment of the transparent support is an alkali saponification treatment.   The optical film according to claim 1, wherein the alignment film is not rubbed.   A polarizing plate comprising the optical film according to claim 1 and a polarizer.   A liquid crystal display device comprising the polarizing plate according to claim 12.   The liquid crystal display device according to claim 13, wherein the driving mode is an IPS format.