JP2007199442A - Optical compensation film, polarizing plate, and liquid crystal display device - Google Patents

Abstract

Provided are an optical compensation film and a polarizing plate which have a good optical compensation ability and have small temperature and humidity dependence of optical characteristics.
A first optically anisotropic layer and a second optically anisotropic layer are included, the in-plane retardation of the first optically anisotropic layer is 0 to 10 nm, and the thickness direction An optical compensation film having a retardation of −400 to −80 nm, an in-plane retardation of the second optically anisotropic layer of 20 to 150 nm, and a retardation in the thickness direction of 100 to 300 nm. An optical compensation film, wherein the second optically anisotropic layer includes a polymer layer containing at least one selected from polyetherketone, polyamide, polyester, polyimide, polyamideimide, and polyesterimide, and the optical compensation It is a polarizing plate having a film and a polarizing film.
[Selection figure] None

Description

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

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

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

  As one means for improving the color tone and the viewing angle of black display, disposing an optical compensation material having birefringence characteristics between the liquid crystal layer and the polarizing plate is also studied in the IPS and FFS modes. For example, by arranging a birefringent medium having an optical axis orthogonal to each other to compensate for 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.

  A polarizing plate is usually produced by laminating a film mainly composed of cellulose triacetate as a protective film on both sides of a polarizing film in which iodine or a dichroic dye is oriented and adsorbed on polyvinyl alcohol. Cellulose triacetate has characteristics such as toughness, flame retardancy, and high optical isotropy (low retardation value), and is widely used as the above-mentioned protective film for polarizing plate. The demand for display performance is becoming strict for liquid crystal display devices, and improvement of environmental resistance, for example, frame-like light leakage (increased transmittance) of liquid crystal display devices due to changes in the surrounding environment (temperature, humidity), that is, Therefore, there is a demand for an improvement against a decrease in display quality of a liquid crystal display device.

  In addition, the protective film for the polarizing film incorporates some or all of the optical compensation function to improve the display quality from the viewpoint of thinning the liquid crystal display device and simplifying the process of attaching the films to the liquid crystal cell. Has been proposed (see, for example, Patent Document 8). A liquid crystal display device having two optical compensation layers and one of the optical compensation layers being a biaxial transparent film has been proposed (see Patent Document 9). According to Patent Document 9, it is described that an optical compensation film having the two optical compensation layers may be incorporated as an integrated polarizing plate with an optical compensation layer by directly bonding the transparent film to a polarizing film. . However, since the optical anisotropy of the optical compensation layer made of the transparent film is large, the environmental resistance is insufficient.

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-A-9-212444 JP 2005-265889 A

  The present invention has been made in view of the above-described problems, and an object thereof is to provide an optical compensation film and a polarizing plate that have a good optical compensation ability and that have a low temperature-humidity dependency of optical characteristics. Another object of the present invention is to provide a high-quality liquid crystal display device in which the contrast reduction and color change depending on the viewing angle are small and the temperature and humidity dependence of the display performance is small.

  The inventor of the present invention diligently studied, and by including a polymer layer containing at least one selected from a specific polymer group in an optically anisotropic layer having predetermined optical characteristics, The knowledge that it can be solved was obtained. More specifically, for example, with respect to an optical compensation film having an optical compensation layer made of a biaxial transparent film, like the optical compensation film described in Patent Document 9, the optical compensation layer includes a specific polymer group. It was found that an optical compensation film excellent in environmental resistance can be provided by including a polymer layer containing at least one selected polymer. As a result of further investigation based on this finding, the present invention has been completed.

Means for solving the above-mentioned problems are as follows.
[1] It includes at least a first optical anisotropic layer and a second optical anisotropic layer, the in-plane retardation of the first optical anisotropic layer is 0 to 10 nm, and the thickness direction An optical compensation film having a retardation of −400 to −80 nm, an in-plane retardation of the second optical anisotropic layer of 20 to 150 nm, and a retardation in the thickness direction of 100 to 300 nm. The second optically anisotropic layer includes an optical compensation film including a polymer layer containing at least one selected from polyether ketone, polyamide, polyester, polyimide, polyamideimide, and polyesterimide.
[2] The optical compensation film according to [1], wherein the polymer layer is obtained by solidifying a development layer of a liquefied solid polymer.
[3] Casting method and extrusion method such as spin coating method, roll coating method, die coating method, flow coating method, printing method, dip coating method, casting film forming method, bar coating method, and gravure printing method. The optical compensation film of any one of [1] or [2], which is a layer formed by a method selected from:
[4] After the polymer layer is formed on the support, the polymer layer is further subjected to one or both of a stretching treatment and a shrinking treatment, whereby the molecules are oriented in the plane and exhibit optical anisotropy. The optical compensation film according to any one of [1] to [3], wherein the support is removed by peeling after the alignment treatment.
[5] The optical compensation film according to any one of [1] to [3], wherein the second optically anisotropic layer further includes a transparent film.
[6] The optical compensation film according to [5], wherein the polymer layer is formed on the transparent film.
[7] After the polymer layer is formed on the transparent film, the polymer layer is further subjected to one or both of a stretching treatment and a shrinking treatment, whereby the molecules are oriented in the plane and exhibit optical anisotropy. An optical compensation film according to [6].
[8] The optical compensation film according to any one of [5] to [7], wherein the in-plane retardation of the transparent film is 0 to 10 nm and the retardation in the thickness direction is -20 to 60 nm.
[9] The optical compensation film according to any one of [5] to [8], wherein the transparent film is a film containing cellulose acylate or cyclic polyolefin.
[10] The first optically anisotropic layer is formed of a composition containing a rod-like liquid crystal compound, and the molecules of the rod-like liquid crystal compound are substantially in a layer plane in the first optically anisotropic layer. The optical compensation film according to any one of [1] to [9], which is fixed in a vertically oriented state.
[11] A polarizing plate having the optical compensation film of any one of [1] to [10] and a polarizing film.
[12] Only a substantially isotropic adhesive layer and / or a substantially isotropic transparent protective film is included between the optical compensation film and the first polarizing film [11]. Polarizing plate.
[13] The polarizing plate according to [12], wherein the transparent protective film is a film containing cellulose acylate or cyclic polyolefin, the in-plane retardation is 0 to 10 nm, and the retardation in the thickness direction is -20 to 20 nm. .
[14] The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and the second optical anisotropic layer is delayed. The polarizing plate according to any one of [11] to [13], wherein the direction of the phase axis and the direction of the absorption axis of the polarizing film are substantially perpendicular to each other.
[15] The second optical anisotropic layer, the first optical anisotropic layer, and the polarizing film are laminated in this order, and the second optical anisotropic layer is delayed. The polarizing plate according to any one of [11] to [13], wherein the direction of the phase axis and the direction of the absorption axis of the first polarizing film are substantially parallel.
[16] A liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate of [14] Including the first optically anisotropic layer, the second optically anisotropic layer, and the polarizing film in this order from the substrate side to the outside of the pair of one substrate, and the second optical The polarizing plate is disposed so that the slow axis of the anisotropic layer and the major axis direction of the liquid crystal molecules during black display are substantially parallel, and a second polarizing film is further provided outside the other substrate. And a liquid crystal display device in which the absorption axes of both polarizing films are orthogonal to each other.
[17] A liquid crystal cell having a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate of [15] The second optical anisotropic layer, the first optical anisotropic layer, and the polarizing film are arranged in this order from the substrate side to the outside of the pair of one substrate, and the second optical The polarizing plate is arranged so that the slow axis of the anisotropic layer and the major axis direction of the liquid crystal molecules at the time of black display are substantially orthogonal, and a second polarizing film is further provided outside the other substrate. A liquid crystal display device in which the absorption axes of both polarizing films are orthogonal to each other.
[18] Only a substantially isotropic adhesive layer and / or a substantially isotropic transparent protective film is included between the second polarizing film and the substrate [16] or [17] The liquid crystal display device.
[19] The liquid crystal display according to [18], wherein the transparent protective film is a film containing cellulose acylate or cyclic polyolefin, the in-plane retardation is 0 to 10 nm, and the retardation in the thickness direction is -20 to 20 nm. apparatus.

  According to the present invention, it is possible to provide an optical compensation film and a polarizing plate that have a good optical compensation ability and have low temperature and humidity dependence of optical characteristics. In addition, according to the present invention, it is possible to provide an IPS and FFS mode liquid crystal display device in which display unevenness due to the influence of temperature and humidity is improved as compared with conventional IPS and FFS mode liquid crystal display devices. It was.

BEST MODE FOR CARRYING OUT THE INVENTION

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

  In the present specification, “parallel” and “orthogonal” mean that the angle is within a range of strictly less than ± 10 °. In this range, an error from a strict angle is preferably less than ± 5 °, and more preferably less than ± 2 °. Further, “substantially vertical” means within a range of less than ± 20 ° from a strict vertical angle. In this range, an error from a strict angle is preferably less than ± 15 °, and more preferably less than ± 10 °. Further, the “slow axis” means a direction in which the refractive index is maximized. Further, the measurement wavelength of the refractive index is a value at λ = 590 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.

[Optical compensation film]
The optical compensation film of the present invention includes at least a first optical anisotropic layer and a second optical anisotropic layer, and the in-plane retardation of the first optical anisotropic layer is 0 to 10 nm. The retardation in the thickness direction is −400 to −80 nm, the in-plane retardation of the second optically anisotropic layer is 20 to 150 nm, and the retardation in the thickness direction is 100 to 300 nm. An optical compensation film, wherein the second optically anisotropic layer includes a polymer layer containing at least one selected from polyether ketone, polyamide, polyester, polyimide, polyamideimide, and polyesterimide. To do.
First, various materials and production methods used for forming the first and second optically anisotropic layers will be described in detail.

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

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

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

  In the first optically anisotropic layer included in the optical compensation film of the present invention, the molecules of the liquid crystal compound are preferably fixed in a predetermined alignment state, preferably in a vertical alignment state. The term “substantially perpendicular to the rod-like liquid crystalline compound” means that the angle formed 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 first optically anisotropic layer contained in the optical compensation film of the present invention may be formed on a support. The first optical anisotropic layer may be provided using the second optical anisotropic layer described later as the support, or after the first optical anisotropic layer is provided on the temporary support, It may be transferred to the polarizing film or the second optically anisotropic layer, or an optically isotropic film may be used as the support. The laminate with the polarizing film or the second optically anisotropic layer can be incorporated into a liquid crystal display device or the like as an optical compensation film.

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

[Bar-shaped liquid crystalline compound]
Examples of the rod-like liquid crystalline compound used for the production of the first optically anisotropic layer include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoates, cyclohexanecarboxylic acid phenyl esters, cyanophenyl. Cyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. It is more preferable to fix the alignment of the rod-like liquid crystal compound by polymerization. As the liquid crystalline compound, those having a partial structure capable of causing polymerization or crosslinking reaction by actinic rays, electron beams, heat, or the like are suitably used. The number of the partial structures is preferably 1 to 6, more preferably 1 to 3. As the polymerizable rod-like liquid crystalline compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, and No. 7-110469. 11-80081, JP 2001-328773, JP 2004-240188, JP 2005-99236, JP 2005-99237, JP 2005-121827, JP It is possible to use the compounds described in 2002-30042 That.

[Vertical alignment accelerator]
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, a composition obtained by adding a compound having an effect of vertically aligning the liquid crystalline compound by an excluded volume effect, an electrostatic effect, or a surface energy effect to the alignment film may be 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. As such a compound (alignment film interface side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystal compound on the alignment film interface side, a pyridinium derivative is preferably used. As a compound (air interface side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystal compound on the air interface side, a fluoro aliphatic group that promotes the uneven distribution of the compound on the air interface side, One or more hydrophilic groups selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. A compound is preferably used. Further, by blending these compounds, for example, when a liquid crystalline composition is prepared as a coating solution, the coating property of the coating solution is improved, and the occurrence of unevenness and repellency is suppressed. The vertical alignment agent will be described in detail below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Formula (II)

In the above formula (II), R ¹¹ , R ¹² and R ¹³ 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 ¹¹ , R ¹² and R ¹³ 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 ¹¹ , R ¹² and R ¹³ 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 ¹¹ , R ¹² and R ¹³ .
The specific structure of L is illustrated below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The preferred range of the content of the fluoropolymer in the 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.

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

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

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

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

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

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

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

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

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

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

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

Next, the formula (III) -b will be described.
R ⁶ has the same meaning as R ⁰ in formula (III) -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) represented by W ³ or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, or a substituent The alkyl group, alkoxy group, or alkylamino group having a carboxyl group, a sulfo group or a phosphonoxy group is a carboxyl group (—COOH) represented by W ¹ and W ² in the above formula (III) -a or a salt thereof, sulfo Group (—SO ₃ H) or a salt thereof, phosphonoxy {—OP (═O) (OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group, or an alkyl having a carboxyl group, a sulfo group, or a phosphonoxy group as a substituent. It is synonymous with an amino group and its preferable range is also the same.

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

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

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

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

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

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

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

  The preferable range of the content of the fluorine-containing compound in the 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 aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Description), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).
It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is more preferable that it is 0.5-5 mass%.

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

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

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

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

  The first optically anisotropic layer is, for example, a coating liquid prepared by dissolving and / or dispersing a liquid crystalline compound and additives such as a polymerization initiator and an alignment controller added as required in a solvent. It can be formed by coating on a support. It is preferable to form an alignment film on a support and apply the coating solution on the surface of the alignment film. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Coating method]
The first optically anisotropic layer can be formed by a known coating method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method). Among these, when the first optically anisotropic layer is formed, it is preferably applied using a wire bar coating method, and the rotational speed of the wire bar preferably satisfies the 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 first 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 first optically anisotropic layer to be formed is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and still more preferably 1 to 5 μm.

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

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

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

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

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

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

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

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

  The alignment film is preferably provided on the transparent support. The alignment film is obtained by crosslinking the polymer layer as described above, but the surface may be rubbed.

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

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

[Support]
As a support for forming the first optically anisotropic layer made of a liquid crystalline compound, a second optically anisotropic layer described later may be used, or the first optical layer may be used on the temporary support. After being provided on the anisotropic layer, it may be transferred to the polarizing film or the second optical anisotropic layer, or an optically isotropic film may be used as the support. When a temporary support is used, the optical properties of the support are not particularly limited, but it is preferable that the first optical anisotropic layer can be easily peeled off. When the first optically anisotropic layer is formed on an optically isotropic support, the support may be removed or left when used in a liquid crystal display device. The support can also be used as a protective film for a polarizing film. The support preferably has a light transmittance of 80% or more.

  As a substantially isotropic support, the in-plane retardation (Re) is preferably 0 to 10 nm, more preferably 0 to 5 nm, and still more preferably 0 to 3 nm. . The retardation in the thickness direction (Rth) is preferably −20 nm to 20 nm, more preferably −15 nm to 15 nm, and still more preferably −10 nm to 10 nm. The wavelength dispersion is preferably such that the ratio of Re400 / Re700 is less than 1.2.

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

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

[Second optically anisotropic layer]
The in-plane retardation of the second optically anisotropic layer is preferably 20 to 150 nm, more preferably 30 to 130 nm, and even more preferably 40 to 110 nm. Furthermore, the retardation in the thickness direction is preferably 100 to 300 nm, more preferably 120 to 280 nm, and still more preferably 140 nm to 260 nm.

  The second optically anisotropic layer is at least one selected from polyetherketone, polyamide, polyester, polyimide, polyamideimide and polyesterimide, preferably polyetherketone (more preferably polyaryletherketone), polyamide And a polymer layer containing at least one selected from polyimide. An example of the second optically anisotropic layer includes a transparent film and a polymer layer obtained by developing a solution prepared by dissolving a solid polymer in a solvent and drying and fixing the solution on the transparent film. is there. In this aspect, the optical properties of both layers are adjusted so that the entire laminate of the transparent film and the polymer layer satisfies the optical properties required for the second optical anisotropic layer. At that time, a polymer liquid is spread on the surface of the transparent film to form the polymer layer, and then one or both of a stretching treatment and a shrinking treatment are performed to orient molecules in the plane of the polymer layer. In-plane optical anisotropy may be developed so that the entire laminate satisfies the above optical characteristics.

[Transparent film]
As the transparent film, a polymer described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having at least one of a substituted imide group and an unsubstituted imide group on a side chain; (B) A film made of a resin composition containing a thermoplastic resin having at least one of a substituted phenyl group and an unsubstituted phenyl group in the side chain and a nitrile group can also be used. Specific examples of such a resin composition include a resin composition containing an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The transparent film may be a film made of a mixed extruded product of the resin composition.

In the second optically anisotropic layer, the smaller the contribution of retardation by the transparent film, the better. As a constituent layer of the second optically anisotropic layer, the optical anisotropy of the transparent film is sufficiently reduced, and a film having Re substantially zero and Rth substantially zero is used as a transparent film. When used, it is possible to further reduce the change in the optical compensation capability depending on the environmental change, and to further improve the light leakage. This is because, for example, when the optical compensation film of the present invention is bonded to a polarizing film and incorporated in a liquid crystal display device as a polarizing plate, the transparent film having the optical characteristics is a buffer layer for stress due to a change in the size of the polarizing film. Thus, it is estimated that the stress strain in the optical compensation layer is reduced. Moreover, since the transparent film itself having such optical characteristics hardly causes light leakage due to stress strain, it is estimated that the light leakage is improved as a whole.
In addition, it is preferable that the second optically anisotropic layer has a transparent film because it can be directly bonded to the polarizing film.

  In order to acquire the said effect, it is preferable that Re and Rth of the said transparent film are substantially 0, Specifically, it is preferable that Re is 0-10 nm, and it is further 0-5 nm. Preferably, it is more preferably 0 to 3 nm, Rth is preferably −20 to 80 nm, further preferably −20 nm to 50 nm, and further preferably −20 nm to 20 nm. The wavelength dispersion is preferably such that the ratio of Re400 / Re700 is less than 1.2.

  From the viewpoint of a material capable of producing a film having a small retardation, the transparent film is preferably a cellulose ester, a polycarbonate, a polysulfone, a polyethersulfone, a polyacrylate, a polymethacrylate, or a cyclic polyolefin. Among them, cellulose ester is preferable, acetyl cellulose is more preferable, and triacetyl cellulose is more preferable. Cyclic polyolefin is also preferable, and obtained by hydrogenating a ring-opening polymer of tetracyclododecenes or a ring-opening copolymer of tetracyclododecenes and norbornenes described in JP-B-2-9619. As a polymer having a polymer as a constituent component, it can be used from the series of Arton (manufactured by JSR), Zeonex, and Zeonore (manufactured by Nippon Zeon).

  The transparent film is preferably formed by a solvent cast method. The thickness is preferably 20 to 500 μm, and more preferably 50 to 200 μm. In order to improve adhesion between the transparent film and the layer (adhesive layer, vertical alignment film or retardation layer) provided on the transparent film, the transparent film is subjected to surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet ray (UV) treatment). , Flame treatment). An adhesive layer (undercoat layer) may be provided on the transparent film. In addition, the transparent film and the long transparent film have an average particle size of about 10 to 100 nm in order to impart slip properties in the transport process or prevent sticking between the back surface and the surface after winding. It is preferable to use what formed the polymer layer which mixed inorganic particle 5%-40% by solid content weight ratio on the one side of the said film by application | coating or co-casting with a film.

[Production of polymer layer]
The polymer layer constituting the second optically anisotropic layer is prepared by dissolving at least one solid polymer selected from polyether ketone, polyamide, polyester, polyimide, polyamideimide and polyesterimide in a solvent. It is a layer formed by spreading the dried solution on the transparent film and drying and fixing it. The developing method varies depending on the viscosity of the developing solution, and when the developing solution has a viscosity in the range of 3.5 to 20 Pa · s, it is preferable to apply the developing solution while applying a shearing force. A comma coat method, a roll coat method, a gravure coat method, etc. can be used. In this case, an optical biaxial birefringent film can be obtained simply by spreading the polymer solution on the transparent film. The optical properties of the birefringent film can be adjusted by, for example, the type and molecular weight of the solid polymer, and can be adjusted by changing the viscosity of the developing solution within the above range (Japanese Patent Laid-Open No. 2005-338425). On the other hand, when the viscosity of the developing solution is smaller than the above range, when the developing solution is only solidified, nx is the in-plane refractive index and nz is the refractive index in the ny thickness direction. Usually, ny> nz and Re is small, and stretching and shrinkage treatment is necessary for the expression of biaxiality. The development method in this case is selected from a spin coating method, a roll coating method, a flow coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, a gravure printing method, and an extrusion method. A method is preferred, and among them, a solution casting method such as a casting method is more preferred from the viewpoint of mass productivity of a film with little thickness unevenness and alignment strain unevenness (Japanese Patent Application Laid-Open No. 2003-315541). The thickness of the polymer layer is preferably 15 μm or less, more preferably 12 μm or less, and even more preferably 2 to 10 μm from the viewpoint of thinning and imparting the desired retardation characteristics.

For the formation of the polymer layer, an appropriate solid polymer capable of forming a layer in which Re is in the range of 0 to 200 nm and Rth is in the range of 0 to 400 nm by the development method can be used. A solid polymer with good heat resistance capable of forming a layer having a light transmittance of 75% or more, particularly 85% or more is preferable, and a negative refractive index that lowers the refractive index in the stretching direction from the viewpoint of stable mass productivity. A solid polymer having birefringence of 2 is more preferred. In the present invention, one or two or more selected from polyether ketone (preferably polyaryl ether ketone), polyamide, polyester, polyimide, polyamideimide and polyesterimide are mixed in view of the development layer forming property and the like. We use what we did.
The solid polymer may be a polymer in which the alignment state of the liquid crystal compound is fixed by means such as polymerization.

  Specific examples of the above-described polyether ketone, particularly polyaryl ether ketone, include those having a repeating unit represented by the following general formula (1) (Japanese Patent Laid-Open No. 2001-49110).

General formula (1)

In the above general formula (1), F represents a fluorine atom, X represents a halogen, an alkyl group or an alkoxy group, and the number of bonds of X to the benzene ring q, that is, a p-tetrafluorobenzoylene group and an oxyalkylene group. The value of the substitution number q of the hydrogen atom at the remaining position where is not bonded is an integer of 0 to 4. R ²¹ is a group represented by the following general formula (2), and m is 0 or 1. Further, n represents the degree of polymerization and is 2 to 5000, with 5 to 500 being preferred.

General formula (2)

  In addition, as a halogen as X in the said General formula (1), a fluorine atom, a bromine atom, a chlorine atom, an iodine atom etc. are mention | raise | lifted, for example, A fluorine atom is especially preferable. Examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. A halogenated alkyl group such as a group, an ethyl group or a trifluoromethyl group thereof is preferred.

  Further, examples of the alkoxy group include C1-C6 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 1-4 linear or branched alkoxy groups, etc. Among them, a halogenated alkoxy group such as a methoxy group, an ethoxy group, or a trifluoromethoxy group thereof is more preferable. In the above, X is particularly preferably a fluorine atom.

  On the other hand, in the group represented by the general formula (2), X ′ is a halogen, an alkyl group or an alkoxy group, and the value of the number of bonds q ′ of X ′ to the benzene ring is an integer of 0 to 4. . Examples of the halogen, alkyl group or alkoxy group as X ′ are the same as those described above for X.

  Preferred X ′ is a fluorine atom, a methyl group or an ethyl group, a halogenated alkyl group such as a trifluoromethyl group thereof, a methoxy group or an ethoxy group, or a halogenated alkoxy group such as a trifluoromethoxy group thereof. Atoms are preferred.

  In the general formula (1), X and X ′ may be the same or different. Further, in the general formulas (1) and (2), two or more X or X ′ present in the molecule based on q or q ′ being 2 or more may be the same or different. Good.

Particularly preferred R ²¹ is a group represented by the following general formula (3).

General formula (3)

In the general formulas (2) and (3), R ²² is a divalent aromatic group, and p is 0 or 1. Examples of the divalent aromatic group include (o, m or p-) phenylene group, naphthalene group, biphenyl group, anthracene group, (o, m or p-) terphenyl group, phenanthrene group, dibenzofuran group, biphenyl. Examples thereof include an ether group, a biphenylsulfone group, and a divalent aromatic group represented by the following formula. In the divalent aromatic group, hydrogen directly bonded to the aromatic ring may be substituted with the halogen, alkyl group or alkoxy group described above.

A preferable divalent aromatic group (R ²² ) is represented by the following formula.

  The polyaryl ether ketone represented by the general formula (1) may be composed of the same repeating unit, or may have two or more different repeating units. In the latter case, each repeating unit may exist in a block form or may exist randomly.

  Based on the above, preferable polyaryl ether ketones represented by the general formula (1) are those represented by the following general formula (4).

General formula (4)

  A preferable polyaryletherketone including a group at the molecular end is represented by the following general formula (5) corresponding to the general formula (1), and corresponds to the general formula (4). Is represented by the following general formula (6). In these, a fluorine atom is bonded to the p-tetrafluorobenzoylene group side in the molecule, and a hydrogen atom is bonded to the oxyalkylene group side.

General formula (5)

General formula (6)

  On the other hand, specific examples of the polyamide or polyester described above include those having a repeating unit represented by the following general formula (7).

General formula (7)

  In the general formula (7), B is halogen, an alkyl group having 1 to 3 carbon atoms or a halide thereof, a phenyl group substituted with one or more of them, or an unsubstituted phenyl group. . z is an integer of 0-3.

E is a covalent bond, an alkenyl group having 2 carbon atoms or a halide thereof, CH ₂ group, C (CX ₃ ) ₂ group, CO group, O atom, S atom, SO ₂ group, Si (R) ₂ group, or NR group.
X in the C (CX ₃ ) ₂ group is a hydrogen atom or a halogen, and R in the Si (R) ₂ group and the NR group is an alkyl group having 1 to 3 carbon atoms or a halide thereof. E is in a meta position or a para position with respect to the carbonyl group or the Y group. Halogen is a fluorine atom, a chlorine atom, an iodine atom or a bromine atom (hereinafter the same in general formula (7)).

  Y is an O atom or an NH group. A is a hydrogen atom, halogen, an alkyl group having 1 to 3 carbon atoms or a halide thereof, a nitro group, a cyano group, a thioalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or a halide thereof, aryl Group or a halide thereof, an alkyl ester group having 1 to 9 carbon atoms, an aryl ester group having 1 to 12 carbon atoms or a substituted derivative thereof, or an arylamide group having 1 to 12 carbon atoms or a substituted derivative thereof.

  N is an integer of 0 to 4, p is an integer of 0 to 3, q is an integer of 1 to 3, and r is an integer of 0 to 3. A preferred polyamide or polyester has a repeating unit represented by the following general formula (8), wherein r and q are 1, and at least one of the biphenyl rings is substituted at the 2-position and the 2′-position. Is.

General formula (8)

  In the general formula (8), m is an integer of 0 to 3, preferably 1 or 2, and x and y are 0 or 1, and are not 0 at the same time. The other symbols have the same meanings as in the case of the general formula (7), but E is a covalent bond in para orientation with respect to the carbonyl group or the Y group.

  In the general formulas (7) and (8), when a plurality of B, E, Y, or A are present in the molecule, they may be the same or different. Similarly, z, n, m, x and y may be the same or different. In this case, B, E, Y, A, z, n, m, x, and y are determined independently.

  The polyamide or polyester represented by the general formula (7) may be composed of the same repeating unit, or may have two or more different repeating units. In the latter case, each repeating unit may exist in a block form or may exist randomly.

  On the other hand, specific examples of the polyimide described above include, for example, a condensation polymerization product of 9,9-bis (aminoaryl) fluorene and an aromatic tetracarboxylic dianhydride, and are represented by the following general formula (9). And those having one or more repeating units.

General formula (9)

  In the general formula (9), R is a hydrogen atom, a halogen, a phenyl group, a phenyl group substituted with 1 to 4 halogens or an alkyl group having 1 to 10 carbon atoms, or 1 to 10 An alkyl group having a carbon atom. Four Rs can be determined independently and can be substituted in the range of 0 to 4. The substituents are preferably those described above, but some of them may be different. Halogen is a fluorine atom, a chlorine atom, an iodine atom or a bromine atom (hereinafter the same in general formula (9)).

Z ¹⁰ is a trisubstituted aromatic group having 6 to 20 carbon atoms. Preferred Z ¹⁰ is a pyromellitic group, a polycyclic aromatic group such as a naphthylene group, a fluorenylene group, a benzofluorenylene group or an anthracenylene group or a substituted derivative thereof, or a group represented by the following general formula (10) It is. Examples of the substituent in the substituted derivative of the polycyclic aromatic group include halogen, an alkyl group having 1 to 10 carbon atoms, or a fluorinated product thereof.

General formula (10)

In the general formula (10), D is a covalent bond, C (R ² ) ₂ group, CO group, O atom, S atom, SO ₂ group, Si (C ₂ H ₅ ) ₂ group, N (R ³ ) ₂ groups or a combination thereof, and m is an integer of 1 to 10. The two R ^{2 s} are each independently a hydrogen atom or a C (R ⁴ ) ₃ group.
Moreover, said two R < ³ > is respectively independently a hydrogen atom, an alkyl group having 1 to about 20 carbon atoms, or an aryl group having about 6 to about 20 carbon atoms. The three R ⁴ are each independently a hydrogen atom, a fluorine atom or a chlorine atom.

  Moreover, what has a unit represented by following General formula (11), (12) as a polyimide other than the above can be mentioned. Especially, the polyimide which has a unit represented by General formula (13) is preferable.

Formula (11)

Formula (12)

Formula (13)

  In the above general formulas (11), (12) and (13), T and L are halogen, phenyl having 1 to 3 carbon atoms or a halide thereof, phenyl substituted by one or more of them. Group or an unsubstituted phenyl group. The halogen is a fluorine atom, a chlorine atom, an iodine atom or a bromine atom (hereinafter the same in general formulas (11), (12) and (13)). z is an integer of 0-3.

G and J are a covalent bond or bond bond, CH ₂ group, C (CX ₃ ) ₂ group, CO group, O atom, S atom, SO ₂ group, Si (C ₂ H ₅ ) ₂ group, or N ( CH ₃ ) group. X in the C (CX ₃ ) ₂ group is a hydrogen atom or halogen (hereinafter the same in general formulas (11), (12) and (13)).

  A is a hydrogen atom, a halogen, an alkyl group or a halide thereof, a nitro group, a cyano group, a thioalkyl group, an alkoxy group or a halide thereof, an aryl group or a halide thereof, or an alkyl ester group or a substituted derivative thereof.

  R is a hydrogen atom, a substituted phenyl group such as a halogen, a phenyl group or a halide thereof, or a substituted alkyl group such as an alkyl group or a halide thereof. n is an integer of 0 to 4, p is an integer of 0 to 3, and q is an integer of 1 to 3.

  In the general formulas (11), (12), and (13), when there are a plurality of T, A, R, or L in the molecule, they may be the same or different. It may be. Similarly, z, n, and m may be the same or different. In this case, T, A, R, L, z, n, and m are determined independently.

  The polyimides represented by the general formulas (9), (11), (12) and (13) may be composed of the same repeating unit, or have two or more different repeating units. It may be. The different repeating unit may be formed by copolymerizing at least one of an acid dianhydride other than the above and a diamine. As the diamine, an aromatic diamine is particularly preferable. When it has the latter different repeating unit, each repeating unit may exist in a block shape or may exist randomly.

  Examples of the acid dianhydride for forming the different repeating units include pyromelt acid dianhydride, 3,6-diphenylpyromelt acid dianhydride, and 3,6-bis (trifluoromethyl) pyromelt acid diacid. Anhydride, 3,6-Dibromopyromelt acid dianhydride, 3,6-dichloropyromelt acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylcarboxylic dianhydride, bis ( 2,3-dicarbophenyl) methane dianhydride.

  Also, bis (2,5,6-trifluoro-3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride (4,4′-oxydiphthalic anhydride), bis (3,4-dicarboxyphenyl) sulfone dianhydride ( 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride), 4,4 ′-[4,4′-isopropylidene-di (p-phenyleneoxy)] bis (phthalic anhydride) Examples of acid dianhydrides are listed.

  Furthermore, N, N- (3,4-dicarboxyphenyl) -N-methylamine dianhydride, bis (3,4-dicarboxyphenyl) diethylsilane dianhydride, 2,3,6,7-naphthalene-tetra Naphthalenetetracarboxylic acids such as carboxylic dianhydrides, 1,2,5,6-naphthalene-tetracarboxylic dianhydrides, 2,6-dichloro-naphthalene-1,4,5,8-tetracarboxylic dianhydrides Acid dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride and pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyridine-2,3,5,6-tetra Heterocyclic aromatic tetracarboxylic dianhydrides such as carboxylic dianhydrides are also examples of the acid dianhydrides.

  Preferably used acid dianhydrides are 2,2′-dibromo-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride and 2,2′-dichloro-4,4 ′, 5,5 ′. -Biphenyltetracarboxylic dianhydrides, 2,2'-substituted dianhydrides such as 2,2'-trihalo-substituted dianhydrides, especially 2,2-bis (trifluoromethyl) -4,4 ' , 5,5'-biphenyltetracarboxylic dianhydride is preferred.

  On the other hand, examples of the diamine for forming the different repeating units include (o, m or p-) phenylenediamine, 2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene, 1,4- Benzenediamine such as diamino-2-phenylbenzene, 1,3-diamino-4-chlorobenzene, 4,4′-diaminobiphenyl, 4,4-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2 , 2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis ( 3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Benzene, and the like.

  4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4′-diaminodiphenylthioether, 4,4′-diaminodiphenylsulfone 2,2′-diaminobenzophenone, 3,3′-diaminobenzophenone, naphthalenediamine such as 1,8-diaminonaphthalene and 1,5-diaminonaphthalene, 2,6-diaminopyridine and 2,4-diaminopyridine, Heterocyclic aromatic diamines such as 1,4-diamino-S-triazine are also examples of the diamines described above.

  Examples of polyimides that can be preferably used include 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4,4′-bis (3,4-dicarboxyphenyl) -2,2-diphenyl. Heat-resistant and solvent-soluble polyimides prepared using aromatic dianhydrides such as propane dianhydride, naphthalenetetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) sulfone dianhydride It is.

  Examples of diamines include 4,4- (9-fluorenylidene) -dianiline, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, and 3,3′-dichloro-4,4′-diamino. Diphenylmethane, 2,2′-dichloro-4,4′-diaminobiphenyl, 2,2 ′, 5,5′-tetrachlorobenzidine, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, etc. A heat-resistant and solvent-soluble polyimide prepared using an aromatic diamine can be preferably used.

  On the other hand, there is no limitation in particular as above-mentioned polyamide imide or polyester imide, One or two or more suitable things can be used. Of these, polyamide imides described in JP-A No. 61-162512 and polyester imides described in JP-A No. 64-38472 can be preferably used.

  As shown in the general formula (9), by introducing a unit in which a disk surface of a ring structure such as a fluorene ring is perpendicular to the main chain, a polymer layer is formed by development and subsequent solidification, and then stretched. In this case, the refractive index in the direction orthogonal to the stretching direction increases, and a film having a large refractive index in the width direction can be obtained by longitudinal uniaxial stretching in the roll film. By using such a film, a polarizing plate having an optical compensation function can be produced by bonding a polarizing film and Roll-to-Roll even with a longitudinally uniaxially stretched film.

  Further, as shown in the general formula (9), the ratio of the unit in which the surface of the ring structure such as a fluorene ring is perpendicular to the main chain and the unit in which the aromatic rings are arranged in the main chain direction is adjusted. Thereby, the wavelength dispersion of the polymer layer formed by development and subsequent solidification can be adjusted.

  The molecular weight of the solid polymer for forming the polymer layer is not particularly limited, but is preferably soluble in a solvent. Above all, the mass average of the polymer layer in terms of film thickness accuracy, surface accuracy or surface smoothness, film strength, prevention of cracking due to expansion and contraction or distortion when formed into a film, and solubility in solvents (preventing gelation) Based on the molecular weight, 10,000 to 1,000,000, particularly 20,000 to 500,000, particularly 50,000 to 200,000 are preferable. The mass average molecular weight is a value measured by gel permeation chromatography (GPC) using polyethylene oxide as a standard sample and a dimethylformamide solvent.

  For the formation of the polymer layer, the above-mentioned polyaryletherketone, polyamide, polyester, polyimide, or other solid polymer may be used alone, or two or more of the same species may be mixed and used. Further, it may be used as a mixture of two or more polymers having different functional groups, such as a mixture of polyaryl ether ketone and polyamide.

  Moreover, you may use together 1 type (s) or 2 or more types of suitable polymers other than the above in the range which the orientation of the said solid polymer which forms a polymer layer does not fall remarkably. Examples of the combined polymer include polyethylene, polypropylene, polystyrene, polymethyl methacrylate, ABS resin and AS resin, polyacetate, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyethersulfone, polyketone, polyimide, poly Examples thereof include thermoplastic resins such as cyclohexanedimethanol terephthalate, polyarylate, and liquid crystal polymer (including a photopolymerizable liquid crystal monomer).

  Thermosetting resins such as epoxy resins, phenol resins, and novolac resins are also examples of the combined polymer. The amount of the combined polymer used is not particularly limited as long as the orientation is not significantly lowered, but is usually 50% by mass or less, particularly 40% by mass or less, particularly 30% by mass or less.

  By using a plurality of polymers in combination as described above, optical anisotropy, wavelength dispersion characteristics, mechanical properties such as strength and elastic modulus, water permeability, planarity, and other layers (for example, the first optical anisotropic layer) ) And other physical properties such as the adhesiveness with the pressure-sensitive adhesive may be adjusted within a preferable range.

  The polymer layer is formed by development of a development layer made of a liquefied solid polymer and subsequent solidification. For liquefaction of the solid polymer, an appropriate method such as a method in which the thermoplastic polymer is heated and melted or a method in which the solid polymer is dissolved in a solvent to form a solution can be employed. Accordingly, the development layer can be solidified by cooling the development layer in the former melt and by drying the solvent after removing the solvent from the development layer. In the developing solution, various additives including stabilizers, plasticizers, metals, and the like can be blended as necessary.

  It is preferable to reduce the film thickness unevenness of the polymer layer because it causes unevenness of Re (λ) and Rth (λ) of the optical compensation film. The film thickness unevenness of the polymer layer can be reduced by adjusting the developing method and adjusting the drying means, and can also be reduced by improving the smoothness of the support on which the polymer layer is developed. By adding a leveling agent to the developing solution for the polymer layer, film thickness unevenness can be significantly reduced. As the leveling agent, a surface active material that lowers the surface tension of the developing solution of the polymer layer is used.

  Examples of such leveling agents include polyethylene glycol type nonionic surfactants such as nonylphenol ethylene oxide adduct and stearic acid ethylene oxide adduct; sorbitan palmitic acid monoester, sorbitan stearic acid monoester, sorbitan stearic acid triester, etc. Polyhydric alcohol type nonionic surfactants; fluorosurfactants such as perfluoroalkylethylene oxide adducts, perfluoroalkylcarboxylates, perfluoroalkylbetaines; alkyl-modified silicone oils, polyether-modified silicone oils, etc. Silicone oil and the like. Specifically, Dispalon LS-009 (manufactured by Enomoto Kasei) is used as the silicone-based surfactant, and Defensor MCF-323, Megafac F-171, F-172, F-177, F- are used as the fluorine-based surfactant. 142D, F-144D, F-140NK (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC-430, FC-170, FC-170C (above, manufactured by Sumitomo 3M), and acrylic surfactant as Disparon L- 1980 (manufactured by Enomoto Kasei), Modaflow (manufactured by Nihon Monsanto) and the like. Moreover, the thing of Unexamined-Japanese-Patent No. 9-230143 can also be used.

  Since the leveling agent has a surface activity, it is often distributed on the surface of the polymer layer. If a leveling agent is present on the surface of the formed polymer layer, for example, when the polymer layer and another layer (for example, a polarizing film or another polymer layer) are bonded with an adhesive, the adhesive and the polymer Adhesiveness with a layer (particularly a polymer layer containing a fluorosurfactant as a leveling agent) may be insufficient, and workability may deteriorate in subsequent rework operations. Therefore, after the polymer layer is formed by development, it is preferable to remove the leveling agent from the surface of the polymer layer. For example, when the leveling agent is washed with an organic solvent or subjected to a saponification treatment, It may be removed during the treatment.

  For the drying of the polymer solution, one or two or more of appropriate methods such as a natural drying (air drying) method or a heat drying method, particularly a heat drying method at 40 to 200 ° C. or a reduced pressure drying method can be employed. In order to reduce thickness unevenness due to drying unevenness at the time of drying, it is preferable that the wind in the environment immediately after the development is laminar, and the wind speed is preferably 1 m / min or less. Further, in order to suppress the occurrence of unevenness in the polymer layer due to the movement of the drying air blown immediately after the development, it is preferable to perform condensation drying without blowing the drying air.

  Solvents used in preparing the developing solution for forming a polymer layer include, for example, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, orthodichlorobenzene, halogenated hydrocarbons; phenol, para Phenols such as chlorophenol; aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N- Ketones such as methyl-2-pyrrolidone; esters such as ethyl acetate and butyl acetate.

  In addition, alcohols such as t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol; dimethylformamide, dimethyl Examples of the solvent include amides such as acetamide; nitriles such as acetonitrile and butyronitrile; ethers such as diethyl ether, dibutyl ether and tetrahydrofuran; methylene chloride, carbon disulfide, ethyl cellosolve and butyl cellosolve.

  A solvent can be used individually or in mixture of 2 or more types in an appropriate combination. From the viewpoint of viscosity at the time of development, the ratio of the solid polymer to 100 parts by mass of the solvent is preferably 2 to 100 parts by mass, more preferably 5 to 50 parts by mass, and 10 to 40 parts by mass. More preferably.

  Of course, a solvent having a function of dissolving the material forming the polymer layer is selected as the solvent, but a solvent that does not violate the support for developing the polymer layer solution is preferably selected.

  As described above, the second optically anisotropic layer as a whole has Re of 20 to 150 nm and Rth of 100 to 300 nm.

  In order to give the solidified polymer layer optical characteristics such as Re, a treatment for orienting molecules in the plane may be further performed. That is, when the viscosity of the developing solution is in the range of 3.5 to 20 Pa · s as described above, desired optical characteristics can be obtained only by the developing method, but the viscosity of the developing solution is smaller than the above range. In order to obtain desired optical properties, a treatment for orienting molecules in the plane is necessary.

  By performing the above-described alignment treatment, the accuracy of the alignment axis in the plane can be increased, and the characteristic of nx> ny> nz can be imparted, and in particular, Re can be increased. Therefore, phase difference characteristics such as Rth and Re can be controlled.

  The orientation treatment can be performed as at least one of an extension treatment and a shrinkage treatment. If the orientation treatment is performed via a transparent film, the polymer layer can be treated with the transparent film supported, and the production efficiency, processing accuracy, etc. In addition, continuous production is possible. The stretching process can be performed as a stretching process, for example. For the stretching treatment, one or two or more suitable methods such as a biaxial stretching method such as a sequential method or a simultaneous method, a uniaxial stretching method such as a free end method or a fixed end method can be applied. From the viewpoint of suppressing the bowing phenomenon, the uniaxial stretching method is preferable.

  On the other hand, the shrinkage treatment can be performed by, for example, a method in which a polymer layer is developed and solidified on a transparent film, and a shrinkage force is applied by utilizing a dimensional change associated with a temperature change of the transparent film. . In that case, it is also possible to use a transparent film imparted with a shrinking ability such as a heat-shrinkable film. At that time, it is desirable to control the shrinkage rate using a stretching machine or the like.

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

  In the first aspect of the polarizing plate of the present invention, the first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and 2 is a polarizing plate in which the direction of the slow axis of the optically anisotropic layer and the direction of the absorption axis of the polarizing film are substantially perpendicular, and the second aspect of the polarizing plate of the present invention is: The second optical anisotropic layer, the first optical anisotropic layer, and the polarizing film are laminated in this order, and the slow axis of the second optical anisotropic layer In the polarizing plate, the direction and the direction of the absorption axis of the polarizing film are substantially parallel. The direction of the slow axis of the second optically anisotropic layer can be adjusted by the stretching process or the shrinking process.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes at least the polarizing plate of the present invention. The liquid crystal display device of the present invention may be any of a reflection type, a semi-transmission type, a transmission type liquid crystal display device and the like. A liquid crystal display device generally includes a polarizing plate, a liquid crystal cell, and a retardation plate, a reflection layer, a light diffusion layer, a backlight, a front light, a light control film, a light guide plate, a prism sheet, a color filter, and the like as necessary. Although comprised from a member, in this invention, there is no restriction | limiting in particular except the point which makes it essential to use the polarizing plate of this invention. 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 of the present invention is preferably used for reflective, transflective, and transmissive liquid crystal display devices. A reflective liquid crystal display device usually 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. As the polarizing plate, the polarizing plate of the present invention can be used. In such a case, the retardation plate may not be separately provided.
The transflective liquid crystal display device includes a liquid crystal cell, a polarizing plate disposed on the viewer side of the liquid crystal cell, and at least one retardation plate disposed between the polarizing plate and the liquid crystal cell. And at least one transflective layer disposed behind the liquid crystal layer as viewed from the viewer, and at least one retardation plate and polarizing plate behind the transflective layer as viewed from the viewer And have. In this type of liquid crystal display device, it is possible to use both a reflection mode and a transmission mode by installing a backlight. Both polarizing plates may be the polarizing plate of the present invention, or only one of them may be the polarizing plate of the present invention. When the polarizing plate of the present invention is arranged, a retardation plate may not be separately arranged between the liquid crystal cell and the polarizing plate of the present invention.

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

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

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

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

The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.
[Example 1]
<Preparation of second optically anisotropic layer>
(Preparation of transparent film (cellulose acetate film) T0)
<< Preparation of cellulose acetate solution >>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution A.
Composition of cellulose acetate solution A ――――――――――――――――――――――――――――――――――――
Cellulose acetate with an acetyl substitution degree of 2.94 100.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass ――――――――――――― ――――――――――――――――――――――

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

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

Optical anisotropy reducing agent

Chromatic dispersion modifier

<< Production of cellulose acetate film >>
94.6 parts by mass of the cellulose acetate solution A, 1.3 parts by mass of the matting agent solution, and 4.1 parts by mass of the additive solution were mixed after filtration, and cast using a band casting machine. The mass ratio of the compound that reduces optical anisotropy and the wavelength dispersion adjusting agent to cellulose acetate in the above composition was 12% and 1.2%, respectively. The film was peeled from the band with a residual solvent amount of 30% and dried at 140 ° C. for 40 minutes to produce a long cellulose acetate film T0 having a thickness of 80 μm. The in-plane retardation (Re) of the obtained film was 1 nm (the slow axis was a direction perpendicular to the film longitudinal direction), and the thickness direction retardation (Rth) was −1 nm.

(Production of polymer layer)
From 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl on the roll film of the transparent film T0. A 15% by weight cyclohexanone solution (viscosity 0.20 Pa · s) of the synthesized polyimide with a weight average molecular weight of 59,000 was continuously applied by a casting method so that the thickness after drying was 5 μm, and 150 ° C. For 10 minutes, and continuously stretched 6% in the conveying direction in an atmosphere at 150 ° C., and then wound up.
When the optical properties of the obtained film were measured using an automatic birefringence meter KOBRA 21ADH (manufactured by Oji Scientific Instruments), the slow axis was perpendicular to the film longitudinal direction, and in-plane retardation was obtained. (Re) was 60 nm, and the thickness direction retardation (Rth) was 200 nm.
The film composed of the transparent film T0 and the polymer layer was used as the second optical anisotropic layer C1.

<Formation of first optically anisotropic layer B1>
A coating solution containing a rod-like liquid crystal compound having the following composition was continuously applied to the surface of the polymer layer of the produced long second optically anisotropic layer C1 with a wire bar of # 5.0. 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., and the alignment of the liquid crystal compound was fixed by UV irradiation to form the first optical anisotropic layer B1.

Composition of coating liquid S1 containing rod-shaped liquid crystal 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 The following fluorine system Polymer 0.4 parts by weight The following pyridinium salt 1 part by weight Methyl ethyl ketone 172 parts by weight ――――――――――――――――――――――――――――――――――― ―――

Rod-shaped liquid crystal compound (I)

Fluoropolymer

Pyridinium salt

  Subsequently, the film prepared in a 1.5 mol / L sodium hydroxide aqueous solution at 55 ° C. was immersed for 2 minutes, and then immersed in water to sufficiently wash away sodium hydroxide. Then, after being immersed for 1 minute in 5 mmol / L sulfuric acid aqueous solution of 35 degreeC, it was immersed in water and the dilute sulfuric acid aqueous solution was fully washed away. Finally, the sample was thoroughly dried at 120 ° C. Thus, an optical compensation film F1 in which the first and second optical anisotropic layers were laminated was produced.

  Only the optically anisotropic layer containing the rod-like liquid crystalline compound was peeled from the produced optical compensation film F1, and the optical properties were measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments). . Re of the optically anisotropic layer alone was 0 nm, and Rth was −260 nm. It was also confirmed that an optically anisotropic layer in which rod-like liquid crystal molecules were aligned substantially perpendicular to the film surface was formed.

<Preparation of polarizing plate P1>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. The surface on which the first optical anisotropic layer of the produced optical compensation film F1 is not formed (that is, the back surface of the transparent film T0) is formed on one surface of the polarizing film, and the surface is saponified on the other surface. The treated cellulose triacetate film T1 (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) was continuously bonded using a polyvinyl alcohol adhesive to produce a long polarizing plate P1. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

<Preparation of polarizing plate P0>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. One side of the polarizing film was saponified with the cellulose acetate film T0, and the other side was saponified with a commercially available cellulose acetate film T1, which was continuously bonded using a polyvinyl alcohol adhesive. P0 was produced.

[Example 2]
<Production of Second Optically Anisotropic Layer C2>
Synthesis from 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl on the roll film of transparent film T0 A 15% by weight cyclohexanone solution of polyimide having a weight average molecular weight of 59,000 was continuously applied by a casting method so that the thickness after drying was 6 μm, dried at 150 ° C. for 10 minutes, and continuously The film was stretched 7% in the width direction by a tenter stretching machine in an atmosphere at 150 ° C. Thereafter, both ends including the portion gripped by the tenter clip were cut off to a width of 1340 mm, knurled in a range of 2 to 12 mm from the end, and wound up.
When the optical properties of the obtained film were measured using an automatic birefringence meter KOBRA 21ADH (manufactured by Oji Scientific Instruments), the slow axis was parallel to the film longitudinal direction, and in-plane retardation ( Re) was 70 nm, and the thickness direction retardation (Rth) was 210 nm.
The film composed of the transparent film T0 and the polymer layer was designated as a second optical anisotropic layer C2.

<Formation of first optically anisotropic layer B1>
In the same manner as in Example 1, an optically anisotropic layer B1 containing a rod-like liquid crystalline compound was formed on the produced long second optically anisotropic layer C2. Further, in the same manner as in Example 1, saponification was performed by dipping in an aqueous sodium hydroxide solution. Thus, an optical compensation film F2 in which the first and second optical anisotropic layers were laminated was produced.

<Preparation of polarizing plate P2>
In the same manner as in Example 1, a long polarizing film was obtained. The surface of the optical compensation film F2 prepared above having the first optical anisotropic layer formed thereon is bonded to one surface of the polarizing film, and the cellulose triacetate film T1 whose surface has been saponified is bonded to the other surface. Thus, a long polarizing plate P2 was produced. At this time, an optically isotropic acrylic pressure-sensitive adhesive was used between the polarizing film and the optical compensation film F2, and a polyvinyl alcohol-based adhesive was used between the polarizing film and the cellulose triacetate film. The absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optically anisotropic layer was 0 °.

[Example 3]
<Formation of first optically anisotropic layer B1>
In the same manner as in Example 1, a long cellulose acetate film T0 was produced. In the same manner as in Example 1, the film surface was subjected to saponification treatment, an alignment film was further formed, and a first optically anisotropic layer B1 was formed thereon using the coating liquid S1. Subsequently, in the same manner as in Example 1, it was immersed in an aqueous sodium hydroxide solution for saponification treatment. In this way, an optical compensation film F3 in which the first optical anisotropic layer was formed on a substantially isotropic support was produced.

<Preparation of polarizing plate P3>
The surface where the first optical anisotropic layer of the produced optical compensation film F3 is not formed on one surface of the long polarizing film obtained in the same manner as in Example 1 (that is, the back surface of the transparent film T0). The cellulose triacetate film T1 whose surface was saponified was bonded to the other surface using a polyvinyl alcohol-based adhesive. Further, the surface of the optical compensation film F3 on which the first optically anisotropic layer is formed and the second optically anisotropic layer C2 including the polymer layer prepared above are isotropic acrylic adhesives. Pasted together. In this manner, a long polarizing plate P3 in which the polarizing film, the first optical anisotropic layer, and the second optical anisotropic layer were laminated in this order was produced. The absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 0 °.

[Example 4]
<Preparation of cyclic polyolefin film C4>
The following composition was put into a mixing tank, stirred to dissolve each component, and then 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.

―――――――――――――――――――――――――――――――――
Cyclic polyolefin solution D4
―――――――――――――――――――――――――――――――――
Cyclic polyolefin: TOPAS 5013 100 parts by weight paraffin wax 135 (Nippon Seiwa Co., Ltd.) 15 parts by weight cyclohexane 380 parts by weight dichloromethane 70 parts by weight --------- ――――――――――――

  Next, the following composition including the cyclic polyolefin solution prepared by the above method was charged into a disperser to prepare a fine particle dispersion M4.

―――――――――――――――――――――――――――――――――
Fine particle dispersion M4
―――――――――――――――――――――――――――――――――
Silica particles having a primary average particle size of 16 nm (aerosil R972 Nippon Aerosil Co., Ltd.) 2 parts by mass cyclohexane 73 parts by mass dichloromethane 10 parts by mass cyclic polyolefin solution D4 10 parts by mass ――――――――――――― ―――――――――――――――――――

  Further, 100 parts by mass of the cyclic polyolefin solution D4 and 1.35 parts by mass of the fine particle dispersion M4 were mixed to prepare a dope for film formation. The above dope was cast using a band casting machine. The film peeled off from the band with a residual solvent amount of about 35% by mass was dried and wound at 120 to 140 ° C. while keeping the film from getting wrinkled. Re was 0.5 nm and Rth was 1 nm. In this way, a cyclic polyolefin film C4 was produced.

<Preparation of polarizing plate P4>
The produced cyclic polyolefin film C4 was bonded to one surface of a long polarizing film obtained in the same manner as in Example 1, and the cellulose triacetate film T1 having a saponified surface was bonded to the other surface. At this time, the polarizing film and the cellulose triacetate film were bonded together using a polyvinyl alcohol-based adhesive, and the polarizing film and the cyclic polyolefin film C4 were bonded together as follows.
Polyester urethane (Mitsui Takeda Chemical Co., Takelac XW-74-C154) 10 parts and isocyanate cross-linking agent (Mitsui Takeda Chemical Co., Takenate WD-725) 1 part are dissolved in water and the solid content is 20%. A solution adjusted to 1 was prepared. Using this as an adhesive, the polarizing film and the cyclic polyolefin film C4 were bonded together and dried and cured in an oven at 40 ° C. for 72 hours to prepare a polarizing plate.

  The surface of the cyclic polyolefin film C4 of the produced polarizing plate and the surface of the optical compensation film F2 on which the first optical anisotropic layer was formed were bonded using an isotropic acrylic pressure-sensitive adhesive. In this way, a long polarizing plate P4 in which the polarizing film, the first optical anisotropic layer, and the second optical anisotropic layer were laminated in this order was produced. The absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 0 °.

[Example 5]
<Formation of Second Optically Anisotropic Layer C5>
On cellulose acetate film T1 (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.), 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2′-bis (trifluoromethyl) A 15 mass% cyclohexanone solution of polyimide having a weight average molecular weight of 59,000 synthesized from -4,4′-diaminobiphenyl was continuously applied by a casting method so that the thickness after drying was 4 μm. The film was dried at 10 ° C. for 10 minutes, continuously stretched in the atmosphere at 150 ° C. for 8% in the conveying direction, and then wound up.
When the optical properties of the obtained film were measured using an automatic birefringence meter KOBRA 21ADH (manufactured by Oji Scientific Instruments), the slow axis was orthogonal to the film longitudinal direction, and Re was 60 nm. Rth was 200 nm. The cellulose acetate film used had an in-plane retardation (Re) of 3.5 nm and a thickness direction retardation (Rth) of 45 nm.
The film composed of the transparent film T1 and the polymer layer was designated as a second optical anisotropic layer C5.
<Formation of first optically anisotropic layer B1>
An optically anisotropic layer B1 containing a rod-like liquid crystalline compound was formed on the long second optically anisotropic layer C5 produced in the same manner as in Example 1. Further, in the same manner as in Example 1, saponification was performed by dipping in an aqueous sodium hydroxide solution. Thus, an optical compensation film F5 in which the first and second optical anisotropic layers were laminated was produced.

<Preparation of polarizing plate P5>
In the same manner as in Example 1, a long polarizing film was obtained. The surface of the optical compensation film F5 prepared above where the first optical anisotropic layer is not formed (that is, the back surface of the transparent film T1) is saponified to the other surface. The treated cellulose triacetate film T1 was continuously bonded using a polyvinyl alcohol-based adhesive to produce a long polarizing plate P5. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

[Example 6]
<Formation of Second Optically Anisotropic Layer C6>
Synthesis from 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl on the roll film of transparent film T0 A 25 mass% cyclohexanone solution (viscosity: 8 Pa · s) of polyimide having a mass average molecular weight of 59,000 was continuously applied using a bar coater so that the thickness after drying was 8 μm, and 10% at 150 ° C. Dried for minutes and wound up.
When the optical properties of the obtained film were measured using an automatic birefringence meter KOBRA 21ADH (manufactured by Oji Scientific Instruments), the slow axis was perpendicular to the film longitudinal direction, and Re was 55 nm. Rth was 190 nm.
The film composed of the transparent film T0 and the polymer layer was designated as a second optical anisotropic layer C6.
<Formation of first optically anisotropic layer B1>
In the same manner as in Example 1, an optically anisotropic layer B1 containing a rod-like liquid crystalline compound was formed on the produced long second optically anisotropic layer C6. Further, in the same manner as in Example 1, saponification was performed by dipping in an aqueous sodium hydroxide solution. Thus, an optical compensation film F6 in which the first and second optical anisotropic layers were laminated was produced.

<Preparation of polarizing plate P6>
In the same manner as in Example 1, a long polarizing film was obtained. The surface on which the first optical anisotropic layer of the produced optical compensation film F6 is not formed (that is, the back surface of the transparent film T0) is saponified on the other surface, and the surface is saponified on the other surface. The treated cellulose triacetate film T1 was continuously bonded using a polyvinyl alcohol-based adhesive to produce a long polarizing plate P6. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

[Example 7]
<Formation of Second Optically Anisotropic Layer C7>
On the roll film of the cyclic polyolefin film C4, from 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl A 25 mass% cyclohexanone solution (viscosity 8 Pa · s) of the synthesized polyimide with a weight average molecular weight of 59,000 was continuously applied using a bar coater so that the thickness after drying was 8 μm, It was dried for 10 minutes and wound up.
When the optical properties of the obtained film were measured using an automatic birefringence meter KOBRA 21ADH (manufactured by Oji Scientific Instruments), the slow axis was perpendicular to the film longitudinal direction, and Re was 55 nm. Rth was 190 nm.
A film comprising this cyclic polyolefin film (transparent film) C4 and a polymer layer was designated as a second optically anisotropic layer C7.
<Formation of first optically anisotropic layer B1>
An optically anisotropic film B7 containing a rod-like liquid crystalline compound was formed on the long second optically anisotropic layer C7 produced in the same manner as in Example 1 to produce an optical compensation film F7.

<Preparation of polarizing plate P7>
In the same manner as in Example 1, a long polarizing film was obtained. The surface of the optical compensation film F7 prepared above where the first optical anisotropic layer is not formed (that is, the surface of the cyclic polyolefin film C4) is formed on one surface of the polarizing film, and the surface is formed on the other surface. Saponified cellulose triacetate film T1 was continuously bonded using a polyvinyl alcohol-based adhesive to prepare a long polarizing plate P7. At this time, the polarizing film and the cellulose triacetate film were bonded together using a polyvinyl alcohol-based adhesive, and the polarizing film and the cyclic polyolefin film C4 were bonded together using an adhesive in the same manner as the polarizing plate P4. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

[Example 8]
<Production of second optically anisotropic layer C8>
On the roll film of the transparent film T0, a 6% by mass NMP (N-methyl-2-pyrrolidone) solution of polyamide (8) represented by the following formula is die coated so that the thickness after drying is 7 μm, The film was continuously applied, dried at 80 ° C. for 1 hour, continuously stretched 7% in the conveying direction in an atmosphere of 150 ° C., and then wound up.
As for the optical properties of the obtained film, the slow axis was orthogonal to the longitudinal direction of the film, the in-plane retardation (Re) was 60 nm, and the retardation in the thickness direction (Rth) was 190 nm.
The film composed of the transparent film T0 and the polymer layer was designated as a second optical anisotropic layer C8.

Polyamide (8)

<Formation of first optically anisotropic layer B1>
In the same manner as in Example 1, an optically anisotropic layer B1 containing a rod-like liquid crystalline compound was formed on the produced long second optically anisotropic layer C8. Further, in the same manner as in Example 1, saponification was performed by dipping in an aqueous sodium hydroxide solution. Thus, an optical compensation film F8 in which the first and second optical anisotropic layers were laminated was produced.

<Preparation of polarizing plate P8>
In the same manner as in Example 1, a long polarizing film was obtained. The surface of the optical compensation film F8 prepared above where the first optical anisotropic layer is not formed (that is, the back surface of the transparent film T0) is saponified to the other surface, and the surface is saponified to the other surface. The treated cellulose triacetate film T1 was continuously bonded using a polyvinyl alcohol-based adhesive to produce a long polarizing plate P8. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

[Example 9]
<Production of Second Optically Anisotropic Layer C9>
On the roll film of the transparent film T0, 4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether and 2,2′-bis (4-hydroxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane, a 27 mass% methyl isobutyl ketone solution of polyaryletherketone is continuously applied by a roll coating method so that the thickness after drying is 7 μm. The film was dried at 1 ° C. for 1 minute, continuously biaxially stretched in an atmosphere at 150 ° C., and then wound up.
As for the optical properties of the obtained film, the slow axis was orthogonal to the longitudinal direction of the film, the in-plane retardation (Re) was 55 nm, and the retardation (Rth) in the thickness direction was 200 nm.
The film composed of the transparent film T0 and the polymer layer was designated as a second optical anisotropic layer C9.
<Formation of first optically anisotropic layer B1>
In the same manner as in Example 1, an optically anisotropic layer B1 containing a rod-like liquid crystalline compound was formed on the produced long second optically anisotropic layer C9. Further, in the same manner as in Example 1, saponification was performed by dipping in an aqueous sodium hydroxide solution. Thus, an optical compensation film F9 in which the first and second optical anisotropic layers were laminated was produced.

<Preparation of polarizing plate P9>
In the same manner as in Example 1, a long polarizing film was obtained. The surface of the optical compensation film F9 prepared above where the first optical anisotropic layer is not formed (that is, the back surface of the transparent film T0) is saponified to the other surface. The treated cellulose triacetate film T1 was continuously bonded using a polyvinyl alcohol-based adhesive to produce a long polarizing plate P9. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

[Comparative Example 1]
<Production of Second Optically Anisotropic Layer (TH1)>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

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

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

Retardation increasing agent (A)

Retardation raising agent B

The obtained dope was cast using a casting machine having a band having a width of 2 m and a length of 65 m. A film having a residual solvent amount of 15% by mass was stretched transversely at a stretch ratio of 20% using a tenter under the conditions of 130 ° C., held at 50 ° C. for 30 seconds with the stretched width, and then clipped to remove cellulose. An acetate film was prepared. The residual solvent amount at the end of stretching was 5% by mass, and further dried to prepare a cellulose acetate film (TH1) with the residual solvent amount being less than 0.1% by mass. The water content of the cellulose acetate film TH1 was 1.6%. In addition, Tg of the used cellulose acylate is 140 degreeC.
The obtained cellulose acetate film TH1 had a width of 1340 mm and a thickness of 88 μm. The in-plane retardation (Re) was 60 nm and the thickness direction retardation (Rth) was 190 nm.

<Formation of first optically anisotropic layer (B1)>
An optically anisotropic layer B1 containing an alignment film and a rod-like liquid crystalline compound was formed on the produced long cellulose acetate film (TH1) in the same manner as in Example 3, followed by saponification treatment. .
In this way, an optical compensation film FH1 in which the second optical anisotropic layer made of a cellulose acetate film and the first optical anisotropic layer were laminated was produced.
<Production of polarizing plate (PH1)>
In the same manner as in Example 1, a long polarizing film was obtained. Cellulose on which the surface of the optical compensation film FH1 produced above is not formed (that is, the back surface of TH1) on one surface of the polarizing film, and the surface is saponified on the other surface. A triacetate film (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) was continuously bonded using a polyvinyl alcohol adhesive to produce a long polarizing plate PH1. At this time, the absorption axis of the polarizing film was parallel to the longitudinal direction, and the angle formed by the absorption axis of the polarizing film and the slow axis of the second optical anisotropic layer was 90 °.

[Example 10]
<Production of liquid crystal display device (L11)>
A liquid crystal cell was taken out from the liquid crystal television TH-32LX500 (manufactured by Matsushita Electric Industrial Co., Ltd.), and the polarizing plate and the optical film which were pasted on the viewer side and the backlight side were peeled off. In this liquid crystal cell, when no voltage was applied and during black display, the liquid crystal molecules were aligned substantially in parallel between the glass substrates, and the slow axis direction was horizontal to the screen.

  The produced polarizing plates (P1 and P0) were bonded to the upper and lower glass substrates of the parallel alignment cell using an adhesive. At this time, P1 is disposed on the polarizing plate on the backlight side, P0 is disposed on the viewer side, and the first optical anisotropic layer included in the polarizing plate P1 is in contact with the glass substrate on the backlight side. Moreover, it bonded together so that the cellulose acetate film T0 contained in polarizing plate P0 might contact the glass substrate by the side of a viewer. Further, the polarizer P1 and the liquid crystal cell were arranged so that the absorption axis of the polarizing plate P1 and the slow axis of the liquid crystal cell were orthogonal, and the absorption axes of the polarizing plate P1 and the polarizing plate P0 were orthogonal. 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, a liquid crystal display device L11 was produced.

[Example 11]
<Production of liquid crystal display device (L12)>
In the same manner as in Example 10, a parallel alignment cell was prepared. The produced polarizing plates (P1 and P0) were bonded to the upper and lower glass substrates of the parallel alignment cell using an adhesive. At this time, P0 is arranged on the polarizing plate on the backlight side, P1 is arranged on the viewer side, and the first optical anisotropic layer included in the polarizing plate P1 is in contact with the glass substrate on the viewer side, Moreover, it bonded together so that the cellulose acetate film T0 contained in the polarizing plate P0 might contact the glass substrate by the side of a backlight. In addition, the absorption axis of the polarizing plate P0 and the slow axis of the liquid crystal cell were made parallel, and the absorption axes of the polarizing plate P0 and the polarizing plate P1 were arranged to be orthogonal. 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, a liquid crystal display device L12 was produced.

[Example 12]
In the production of the liquid crystal display device L11 of Example 10, the polarizing plate P2, P3, P4, P5, P6, P7, P8, P9 and the polarizing plate PH1 of the comparative example were used instead of the polarizing plate P1, and the liquid crystal display device. Were made L21, L31, L41, L51, L61, L71, L81, L91, and LH11, respectively. However, about the polarizing plates P2-P9, it arrange | positioned so that the 2nd optically anisotropic layer contained in each might contact | connect the glass substrate side of a backlight side.

[Example 13]
In the production of the liquid crystal display device L12 of Example 11, the polarizing plate P2, P3, P4, P5, P6, P7, P8, P9 and the polarizing plate PH1 of the comparative example were used instead of the polarizing plate P1, and the liquid crystal display device. Were made L22, L32, L42, L52, L62, L72, L82, L92 and LH12, respectively. However, about the polarizing plates P2-P9, it arrange | positioned so that the 2nd optically anisotropic layer contained in each might contact | connect the glass substrate side at the side of a viewer.

  The manufactured liquid crystal display was turned on and black was displayed on the entire screen. Comparison was made immediately after lighting and after lighting for 500 hours in an environment of temperature 30 ° C. and humidity 80% RH. Immediately after lighting, the liquid crystal display device using the polarizing plates (P1 to P9) of the example and the liquid crystal display devices (LH11, LH12) using the polarizing plate (PH1) of the comparative example are observed in substantially the same manner. After 500 hours, light leakage at the four corners of the screens of L11, L12, L21, L22, L31, L32, L41, L42, L61, L62, L71, L72, L81, L82, L91, and L92 was almost observed. Although not, light leakage was slightly observed in L51 and L52, and light leakage was clearly observed in LH11 and LH12.

Claims (19)

It includes at least a first optical anisotropic layer and a second optical anisotropic layer, the in-plane retardation of the first optical anisotropic layer is 0 to 10 nm, and the retardation in the thickness direction is An optical compensation film having a retardation of -400 to -80 nm, an in-plane retardation of the second optical anisotropic layer of 20 to 150 nm, and a retardation in the thickness direction of 100 to 300 nm, An optical compensation film comprising a polymer layer in which the second optical anisotropic layer includes at least one selected from polyether ketone, polyamide, polyester, polyimide, polyamideimide, and polyesterimide. The optical compensation film according to claim 1, wherein the polymer layer is obtained by solidifying a development layer of a liquefied solid polymer. The polymer layer is selected from a casting method such as a spin coating method, a roll coating method, a die coating method, a flow coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, a gravure printing method, and an extrusion method. The optical compensation film according to claim 1, which is a layer formed by the method. After the polymer layer is formed on the support, the polymer layer is further subjected to one or both of stretching treatment and shrinking treatment, whereby the molecules are oriented in a plane and express optical anisotropy. The optical compensation film according to claim 1, wherein the support is removed by peeling after the treatment. The optical compensation film according to claim 1, wherein the second optically anisotropic layer further contains a transparent film. The optical compensation film according to claim 5, wherein the polymer layer is formed on the transparent film. The polymer layer is a layer that is formed on the transparent film and further subjected to one or both of a stretching treatment and a shrinking treatment, whereby molecules are oriented in a plane and optical anisotropy is expressed. 6. The optical compensation film according to 6. The optical compensation film according to any one of claims 5 to 7, wherein the in-plane retardation of the transparent film is 0 to 10 nm and the retardation in the thickness direction is -20 to 60 nm. The optical compensation film according to claim 5, wherein the transparent film is a film containing cellulose acylate or cyclic polyolefin. The first optically anisotropic layer is formed from a composition containing a rod-like liquid crystal compound, and the molecules of the rod-like liquid crystal compound are substantially perpendicular to the layer plane in the first optically anisotropic layer. The optical compensation film according to claim 1, which is fixed in an oriented state. The polarizing plate which has an optical compensation film of any one of Claims 1-10, and a polarizing film. 12. The substantially optically isotropic adhesive layer and / or only the substantially isotropic transparent protective film is included between the optical compensation film and the first polarizing film. Polarizer. The polarizing plate according to claim 12, wherein the transparent protective film is a film containing cellulose acylate or cyclic polyolefin, and has an in-plane retardation of 0 to 10 nm and a retardation in the thickness direction of -20 to 20 nm. The first optical anisotropic layer, the second optical anisotropic layer, and the polarizing film are laminated in this order, and the slow axis of the second optical anisotropic layer The polarizing plate according to claim 11, wherein the direction and the direction of the absorption axis of the polarizing film are substantially orthogonal to each other. The second optical anisotropic layer, the first optical anisotropic layer, and the polarizing film are laminated in this order, and the slow axis of the second optical anisotropic layer The polarizing plate according to claim 11, wherein the direction and the direction of the absorption axis of the first polarizing film are substantially parallel. A liquid crystal cell comprising a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate according to claim 14. The first optically anisotropic layer, the second optically anisotropic layer, and the polarizing film are arranged in this order from the substrate side to the outside of the pair of one substrate, and the second optically anisotropic layer. The polarizing plate is arranged so that the slow axis of the isotropic layer and the major axis direction of the liquid crystal molecules at the time of black display are substantially parallel, and a second polarizing film is further provided outside the other substrate. A liquid crystal display device in which the absorption axes of both polarizing films are orthogonal to each other. A liquid crystal cell comprising a pair of substrates and a liquid crystal layer in which liquid crystal molecules sandwiched between the pair of substrates are aligned substantially parallel to the substrate during black display, and the polarizing plate according to claim 15. The second optically anisotropic layer, the first optically anisotropic layer, and the polarizing film are arranged in this order from the substrate side to the outside of the pair of one substrate, and the second optically anisotropic layer. The polarizing plate is disposed so that the slow axis of the isotropic layer and the major axis direction of the liquid crystal molecules during black display are substantially perpendicular to each other, and a second polarizing film is further provided outside the other substrate. A liquid crystal display device in which the absorption axes of both polarizing films are orthogonal to each other. 18. Only a substantially isotropic adhesive layer and / or a substantially isotropic transparent protective film is included between the second polarizing film and the substrate. Liquid crystal display device. 19. The liquid crystal display device according to claim 18, wherein the transparent protective film is a film containing cellulose acylate or cyclic polyolefin, and has an in-plane retardation of 0 to 10 nm and a thickness direction retardation of -20 to 20 nm. .