KR20070035983A - Optical compensation sheet, polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

assignment

The optical compensation sheet which contributes to the reduction of the leakage light and color change from the inclination direction of the liquid crystal display device, especially the liquid crystal display device in the IPS mode or the FFS mode, for example, 60 °, and the improvement of the front contrast, etc. to provide.

Resolution

An optical compensation sheet which has at least two types of optically anisotropic layers containing a liquid crystalline compound having at least one polymerizable group in one molecule, and wherein the number of the polymerizable groups each has a liquid crystalline compound.

Optical Compensation Sheet, Polarizer, Liquid Crystal Display

Description

Optical compensation sheet and polarizing plate and liquid crystal display device using the same {OPTICAL COMPENSATION SHEET AND, POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME}

1 is a schematic view of a liquid crystal cell of an ISP mode produced in Comparative Example 1-1.

* Description of the sign *

1: liquid crystal element pixel region

2: pixel electrode

3: display electrode

4: rubbing direction

5a, 5b: director of the liquid crystal compound in black display

6a, 6b: director of the liquid crystal compound at the time of white display

[Patent Document 1] Japanese Patent Application Laid-Open No. 9-80424

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-133408

[Patent Document 3] Japanese Patent Application Laid-Open No. 11-305217

[Patent Document 4] Japanese Patent Application Laid-Open No. 10-307291

The present invention belongs to the field of novel optical compensation sheets, and polarizing plates and liquid crystal displays using the same. This invention belongs also to the technical field of the method of controlling the orientation order of a liquid crystalline compound. In addition, the present invention relates to the technical field of a liquid crystal display device, and more particularly, to an in-plane switching (IPS) mode or an FFS mode liquid crystal display device which is displayed by applying a lateral electric field to a liquid crystal compound oriented in the horizontal direction. will be.

As a liquid crystal display device, the so-called TN mode is widely used as a method of applying an electric field in a direction perpendicular to a substrate with a liquid crystal layer in which a nematic liquid crystal is arranged between two orthogonal polarizing plates. In this system, since the liquid crystal rises with respect to the substrate during black display, when viewed obliquely, birefringence occurs due to the liquid crystal compound, and light leakage occurs. For this problem, a method of optically compensating the liquid crystal cell and preventing this light leakage by using a film in which the liquid crystal compound is hybrid oriented has been put into practical use. However, even when the liquid crystal compound is used, it is very difficult to completely optically compensate the liquid crystal cell without any problem, causing a problem that the seaweed inversion in the downward direction of the screen cannot be completely suppressed.

In order to solve such a problem, a liquid crystal display device in which a transverse electric field is applied to a liquid crystal, a so-called IPS mode or a FFS mode, or a projection or slit electrode formed in a panel by vertically aligning a liquid crystal having a dielectric constant anisotropy The vertical orientation (VA) mode which carried out the orientation division by this is proposed, and is utilized. In recent years, these panels are not only used for monitors, but are being developed as televisions. As a result, screen brightness is greatly improved. For this reason, some light leakage in the diagonal inclination-incidence direction at the time of black display which did not become a problem conventionally in these operation modes has been made current as a cause of the display quality fall.

As one of means for improving the viewing angle of this color tone or black display, disposing an optical compensation material having birefringence property between the liquid crystal layer and the polarizing plate is also examined in the IPS and FFS modes. For example, when a birefringent medium orthogonal to each other is arranged between the substrate and the polarizing plate having an optical axis having a function of compensating the increase and decrease of the retardation of the liquid crystal layer at the time of inclination, the white display or the halftone display is directly viewed in the inclined direction. It is disclosed that the coloring can be improved (see Patent Document 1). Moreover, as an optical compensation film, the method of combining the film | membrane in which birefringence is positive and an optical axis in-plane of a film, and the film | membrane in which birefringence is positive and an optical axis in the normal direction of a film (refer patent document 2), retardation A method of using a biaxial optical compensation sheet having 1/2 wavelength (see Patent Document 3), a method of forming an optical compensation layer having positive retardation on this surface by using a film having negative retardation as a polarizing plate protective film ( Patent Document 4) has been proposed.

However, when optically compensating an IPS mode or FFS mode liquid crystal cell using an optical compensating sheet made of a stretched birefringent polymer film, it is necessary to use a plurality of films, and as a result, the thickness of the optical compensating sheet is increased to display It is disadvantageous for thinning the device. Moreover, also in the method of turning off a liquid crystal using the optically anisotropic layer formed from the discotic liquid crystalline compound etc. which solved this problem, when a discotic liquid crystalline compound is orientated horizontally with respect to a board | substrate surface, an orientation defect tends to generate | occur | produce. In addition, when used in a liquid crystal display device, light incident obliquely into the diffused light of the backlight easily dissipates to the front by eliminating polarization in a film having a large front Re, and light leakage occurs during black display, whereby a phase difference film with low extinction is produced. Also, problems such as lowering of contrast occurred.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and contributes to the reduction of leakage light and color change from an inclination direction, for example, 60 °, of a liquid crystal display device, especially an IPS mode or FFS mode liquid crystal display device. An object of the present invention is to provide an optical compensation sheet and a polarizing plate that contribute to the improvement of front contrast. Another object of the present invention is to provide a liquid crystal display device having a low black brightness and an improved front contrast ratio, particularly a liquid crystal display device having an IPS mode.

Means to solve the problem

Means for solving the above problems are as follows.

(1) The optical compensation sheet which has an optically anisotropic layer containing the liquid crystalline compound which has one or more polymeric groups in at least 2 types of one molecule, and differs in the number of polymeric groups which each said liquid crystalline compound has.

(2) The said optically anisotropic layer contains two types of liquid crystalline compounds whose number of polymerizable groups which the said liquid crystalline compound has m and n (m and n are respectively positive integers and m> n), The said optical S (m, n), when the orientation order diagram of the optically anisotropic layer which removed the liquid crystalline compound whose number of polymeric groups is n from this optically anisotropic layer is set to S (m), S (m, n) The optical compensation sheet as described in (1) which is S (m).

(3) The said optically anisotropic layer contains two types of liquid crystalline compounds whose number of polymeric groups which the said liquid crystalline compound has m and n (m and n are respectively positive integers and m> n), The said optical When the degree of polymerization of the anisotropic layer is P (m, n) and the degree of polymerization of the optically anisotropic layer from which the number of polymerizable groups is n is removed from the optically anisotropic layer is P (m), P (m, n) <P (m) The optical compensation sheet as described in (1) or (2) which is phosphorus.

(4) The optical compensation sheet in any one of (1)-(3) whose polymerizable group which the said liquid crystalline compound has is an acrylate group and / or a methacrylate group.

(5) The optical compensation sheet in any one of (1)-(4) whose number of polymeric groups which the said liquid crystalline compound has is an integer of 1-4.

(6) The said optically anisotropic layer contains two types of liquid crystalline compounds whose number of polymeric groups which the said liquid crystalline compound has m and n (m and n are respectively positive integers and m> n), The said optical When the mass parts of the liquid crystal compound contained in the anisotropic layer are W (m) and W (n), the adhesion of the optically anisotropic layer and the support when satisfying W (m) ≥ W (n) is a test of JIS K 5400 standard. The optical compensation sheet in any one of (1)-(5) which is 6 or more.

(7) Furthermore, the optically anisotropic layer has a support, wherein the liquid crystalline compound is oriented in any one of a homeotropic orientation, a homogeneous orientation, a hybrid orientation, a cholesteric liquid crystal orientation, and a monoaxial tilt orientation, The optical compensation sheet in any one of 1)-(6).

(8) Furthermore, as described in any one of (1)-(6) which has a support body, the said liquid crystalline compound is a rod-like liquid crystalline compound, and this rod-shaped liquid crystalline compound is homeotropically oriented. Optical compensation sheet.

(9) The liquid crystal compound is aligned and fixed in the range of 40 to 100 ° C, and the optically anisotropic layer is 0.12 ≦ Rth / d ≦ 0.24 (where Rth is a retardation in the thickness direction of the optically anisotropic layer, d is a liquid crystal). The optical compensation sheet in any one of (1)-(8) which satisfy | fills the film thickness of a compound).

The optical compensation sheet in any one of (1)-(9) in which the said optically anisotropic layer contains the polymer containing the repeating unit represented by following General formula (1).

General formula (1)

(In General Formula (1), R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent. L is a combination of two or more selected from the following divalent linking groups selected from the following linking group or the following linking group. The divalent linking group formed by this is shown.

(Connector group)

Single bond, -O-, -CO-, -NR ^4- (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), -S-, -SO _2- , -P (= O) (OR ⁵ )-(R ⁵ represents an alkyl group, an aryl group or an aralkyl group), an alkylene group and an arylene group

Q represents a carboxyl group (-COOH) or a salt thereof, a sulfo group (-SO ₃ H) or a salt thereof, or a phosphonoxy {-OP (= 0) (OH) ₂ } or a salt thereof.)

(11) In any one of (1)-(9) in which the said optically anisotropic layer contains the polymer containing the repeating unit represented by following General formula (1), and the repeating unit derived from a fluoroaliphatic group containing monomer. The optical compensation sheet described.

General formula (1)

(In General Formula (1), R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent. L is a combination of two or more selected from the following divalent linking groups selected from the following linking group or the following linking group. The divalent linking group formed by this is shown.

(Connector group)

Single bond, -O-, -CO-, -NR ^4- (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), -S-, -SO _2- , -P (= O) (OR ⁵ )-(R ⁵ represents an alkyl group, an aryl group or an aralkyl group), an alkylene group and an arylene group

Q represents a carboxyl group (-COOH) or a salt thereof, a sulfo group (-SO ₃ H) or a salt thereof, or a phosphonoxy {-OP (= 0) (OH) ₂ } or a salt thereof.)

(12) The optical compensation sheet according to any one of (1) to (11), in which the optically anisotropic layer contains at least one kind of onium salt.

(13) Furthermore, Re has a support body, Re measured from the normal line direction of the said support body is 20 nm-150 nm, Rth of the said support body is 100 nm-300 nm, and Re of the said optically anisotropic layer is 20 nm or less. The optical compensation sheet in any one of (1)-(12) whose Rth of the said optically anisotropic layer is -400 nm--80 nm.

(14) The polarizing plate which has the optical compensation film in any one of (1)-(13), and a polarizing film.

(15) A polarizing plate having at least an optical compensation sheet according to (13) and a polarizing film and laminated in the order of the optically anisotropic layer, the support and the polarizing film, wherein the slow axis direction of the support and the absorption axis of the polarizing film Polarizing plate whose direction is substantially orthogonal.

(16) A polarizing plate having at least an optical compensation sheet according to (13) and a polarizing film and laminated in the order of the optically anisotropic layer, the support and the polarizing film, wherein the slow axis direction of the support and the absorption axis of the polarizing film Polarizers whose directions are substantially parallel.

(17) a liquid crystal cell having a pair of substrates, a liquid crystal layer in which liquid crystal molecules sandwiched by the pair of substrates are oriented substantially parallel to the substrate during black display, a first polarizing plate, and a second polarizing film Have,

The said 1st polarizing plate is a polarizing plate as described in (15),

The first polarizing plate is formed so that the optically anisotropic layer side is the substrate side, and the long axis direction of the slow axis of the support and the liquid crystal molecules at the time of black display are substantially parallel to one outside of the pair of substrates. Is arranged to be

Moreover, the liquid crystal display device in which the said 2nd polarizing film is formed so as to mutually orthogonally cross with the absorption axis of the polarizing film of the said 1st polarizing plate on the other outer side of the said pair of board | substrates.

(18) A liquid crystal cell having a pair of substrates and a liquid crystal layer in which the liquid crystal molecules sandwiched by the pair of substrates are oriented substantially parallel to the substrate at the time of black display, a first polarizing plate, and a second polarizing film ,

The first polarizing plate is the polarizing plate described in (16),

The first polarizing plate is formed so that the optically anisotropic layer side is the substrate side, and the long axis direction of the slow axis of the support and the liquid crystal molecules at the time of black display are substantially parallel to one outside of the pair of substrates. Is arranged to be

Moreover, the liquid crystal display device in which the said 2nd polarizing film is formed so as to mutually orthogonally cross with the absorption axis of the polarizing film of the said 1st polarizing plate on the other outer side of the said pair of board | substrates.

(19) The liquid crystal display device according to (17) or (18), wherein only the substantially isotropic adhesive layer and / or the substantially isotropic transparent protective film are included between the second polarizing film and the substrate.

(20) The liquid crystal display device according to (19), wherein the transparent protective film is a cellulose acetate film satisfying the following formulas (I) and (II):

(I): 0≤Re (630) ≤10 and Rth (630) │25

(II): Re (400) -Re (700) │≤10 and Rth (400) -Rth (700) │≤35

[Wherein Re (λ) is the front retardation value (unit: nm) at wavelength λ nm, and Rth (λ) is the retardation value (unit: nm) in the film thickness direction at wavelength λ nm.

To practice the invention  Best form for

Hereinafter, the present invention will be described in detail. Although description of the element | module described below is based on typical embodiment of this invention, this invention is not limited to such embodiment. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in this specification, "substantially orthogonal" and "substantially parallel" refer to the positional relationship permitted in the range of 90 degrees +/- 5 degrees and 0 degrees +/- 5 degrees when each positional relationship is limited to an angle. It does not mean that it is 90 ° and 0 °, which are strictly geometric positional relationships.

In addition, substantially isotropic in this specification means that the absolute value of a phase difference is 5 nm or less in either direction.

In this specification, Re ((lambda)) and Rth ((lambda)) represent the in-plane retardation in the wavelength (lambda), and the retardation of the thickness direction, respectively. Re ((lambda)) is measured by injecting light of wavelength (lambda) nm in a film normal line direction in KOBRA 21ADH or WR (Oji Measurement Instruments Co., Ltd. product). Rth (λ) refers to Re (λ) as the in-plane slow axis (determined by KOBRA 21ADH or WR) as the inclination axis (rotation axis) (if there is no ground axis, any direction in the film plane is the rotation axis). 6 points are measured by injecting light having a wavelength of λnm in the inclination direction in 10 degree steps from the normal direction to the 50 degree one side with respect to the film normal direction, and measuring all 6 points of the measured retardation value and the average refractive index. Based on the calculated film thickness value, KOBRA 21ADH or WR is calculated. In addition, the retardation value is measured from two arbitrary directions by making a slow axis into an inclination axis (rotation axis) (when there is no ground axis, and using any direction in a film plane as a rotation axis), and the hypothetical value of the value and an average refractive index. And based on the input film thickness value, Rth can also be computed from following formula (1) and formula (2). Here, the assumption of the average refractive index may be a polymer handbook (JOHN WlLEY & SONS, INC) and values of catalogs of various optical films. If the value of the average refractive index is not already known, it can be measured with an Abbe refractometer. The value of the average refractive index of the main optical film is illustrated below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), polystyrene (1.59). By inputting the assumption values and film thicknesses of these average refractive indices, KOBRA 21ADH or WR calculates nx, ny, nz. From this calculated nx, ny, and nz, Nz = (nx-nz) / (nx-ny) is further calculated.

Formula (1)

Said Re ((theta)) shows the retardation value Re in the direction which inclined angle (theta) in a normal direction.

Formula (2)

Rth = ((nx + ny) / 2-nz) × d

In addition, in this specification, a "ground axis" means the direction in which a refractive index becomes largest. In addition, in this specification, unless otherwise indicated, a "polarizing plate" is used by the meaning containing both a long polarizing plate and the polarizing plate cut | disconnected in the magnitude | size inserted in a liquid crystal device. In addition, in this specification, although a "polarizing film" and a "polarizing plate" are distinguished and used, a "polarizing plate" shall mean the laminated body which has a transparent protective film which protects this polarizing film on at least one surface of a "polarizing film."

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the optical compensation sheet of this invention is described in detail.

The preferable structure of the optically anisotropic layer in the optical compensation sheet of this invention is an optical compensation sheet which has an optically anisotropic layer containing a specific liquid crystalline compound. In particular, it is preferable that it is an optical compensation sheet which arrange | positioned the optically anisotropic layer on a support body.

It is preferable to use a discotic liquid crystalline compound or a rod-like liquid crystalline compound, and, as for the liquid crystalline compound in the optical compensation sheet of this invention, it is more preferable to use a rod-like liquid crystalline compound. . As for the orientation form of a liquid crystalline compound, any of homeotropic orientation, homogeneous orientation, hybrid orientation, and uniaxial tilt orientation is preferable. Here, the hybrid orientation is, for example, increased in the direction of the long axis of the liquid crystalline compound (disc surface in the discotic liquid crystalline compound) and the angle of the surface of the support, that is, the inclination angle, in the direction of the depth of the optically anisotropic layer (perpendicular to the support) or I say that it is decreasing. In addition, uniaxial inclination orientation is, for example, the long axis of the liquid crystal compound (the disc surface in the discotic liquid crystal compound) and the angle of the surface of the support, that is, the inclination angle θ (0 <θ <90 °) is the depth of the optically anisotropic layer. It is said to be constant in the direction (perpendicular to the support).

In the present invention, the rod-shaped liquid crystalline compound is formed, the orientation form is more preferably homeotropic alignment or hybrid orientation, and more preferably homeotropic alignment.

[Liquid crystalline compound]

The liquid crystalline compound employ | adopted for the optical compensation sheet of this invention is at least two types, and contains the liquid crystalline compound which has one or more polymerizable groups in 1 molecule. In addition, the number of the polymerizable groups which this liquid crystal compound has respectively differs. Although the kind of liquid crystalline compound which has a polymeric group is not specifically limited, The liquid crystalline compound which has 1-5 acrylate groups and / or methacrylate groups, respectively is preferable, and the liquid crystalline compound which has 1-4 pieces is more preferable. Preferably, the liquid crystalline compound which has 1-2 acrylate group and / or methacrylate group is more preferable. Particular preference is given to rod-like liquid crystalline compounds each having an acrylate group. By setting it as 1 or more, since the order of order decreases but polymerizable groups increase, adhesiveness improves and it is preferable. By setting it as five or less, since the orientation order tends to increase, it is preferable. Moreover, it is preferable that the optically anisotropic layer contains the liquid crystalline compound which has the same polymeric group, It is preferable that acrylate group has two or more rod-shaped liquid crystal compounds from which 1-4 polymeric groups differ, and 1-2 are preferable. It is more preferable that two polymerizable groups have two or more rod-shaped liquid crystal compounds.

It is preferable that the liquid crystalline compound in this invention contains two types of liquid crystalline compounds whose number of polymeric groups which this liquid crystalline compound has m and n. Here, m and n are respectively positive integers and m> n. Furthermore, the content of the compound having the number of polymerizable groups n is preferably 50% by weight or less, more preferably 1.0 to 10% by weight of the content of the compound having the number of polymerizable groups m. In particular, even if more than 50% of the liquid crystal compound having one acrylate group is added to the rod-like liquid crystal compound having two acrylate groups with respect to the total weight of the rod-shaped liquid crystal compound, the orientation order is improved, but two acrylic As the content of the rod-like liquid crystal compound having a rate group decreases, the degree of polymerization of the optically anisotropic layer decreases, and the adhesion to the support tends to deteriorate. Therefore, in order to maintain adhesiveness, it is preferable to add 0.5-50 weight% of rod-shaped liquid crystalline compounds which have one acrylate group with respect to the total weight of a rod-shaped liquid crystalline compound, and to make it 0.5 to 20 weight%. More preferably, the degree of polymerization thereof is preferably at least 85% or more, and 90% or more becomes a more preferable value.

Moreover, a high molecular liquid crystalline compound may be sufficient as the liquid crystal compound in this invention, and a low molecular liquid crystalline compound may be sufficient as it. Furthermore, it is preferable to be fixed in the orientation state. The liquid crystal compound in the present invention includes those which are crosslinked at the time of forming the optically anisotropic layer and do not exhibit the liquid crystal.

[Bar-shaped liquid crystalline compound]

As a rod-shaped liquid crystalline compound in this invention, azomethine, azoxy, cyano biphenyl, cyano phenyl ester, benzoic acid ester, cyclohexane carboxylic acid phenyl ester, cyano phenyl cyclohexane , Cyano substituted phenylpyrimidines, alkoxy substituted phenylpyrimidines, phenyldioxanes, tolans and alkenylcyclohexylbenzonitriles are preferably used. The rod-like liquid crystalline compound also includes a metal complex. Moreover, the liquid crystal polymer which contains a rod-shaped liquid crystalline compound in a repeating unit can also be used as a rod-shaped liquid crystalline compound in this invention. In other words, the rod-like liquid crystal compound may be combined with the (liquid crystal) polymer. For the rod-shaped liquid crystalline compound, for example, Chapter 4, Chapter 7 and Chapter 11 of the Quarterly Chemistry Summary Volume 22 Liquid Crystal Chemistry (1994) Nippon Chemical Society, and the 142 Committee of the Liquid Crystal Device Handbook The thing described in Chapter 3 can be employ | adopted.

It is preferable that the birefringence of the rod-like liquid crystal compound is in the range of 0.001 to 0.7.

[Polymerizable Liquid Crystal Compound]

The polymerizable liquid crystal compound is not particularly limited as long as it is immobilized by a polymerization reaction. For example, it is preferable that it is a liquid crystalline compound which has a polymeric group of [Formula 11] and [Formula 12] of Paragraph No. 0049-0050 of Unexamined-Japanese-Patent No. 2004-339193. Especially, the liquid crystalline compound which has an acrylate group and / or a methacrylate group is especially preferable. As a specific example of the rod-shaped liquid crystalline compound which has one or two acrylate groups and / or a methacrylate group, Paragraph No. 0082-0105 of Unexamined-Japanese-Patent No. 8-3111, Unexamined-Japanese-Patent No. Paragraphs [0022] to [0040] of Japanese Patent Application Laid-Open No. 9-281331, paragraphs [0115] to [0128] of JP 2000-281628, paragraphs [0250] to [0400] of JP 2002-220421 A And the compounds described in paragraphs [0056] to [0075] of JP-A-2003-48903. About two or more polymeric liquid crystal compounds, the compound of Unexamined-Japanese-Patent No. 2002-30042 is mentioned. However, the rod-shaped liquid crystalline compound which has one or two acrylate groups and / or methacrylate groups used for this invention is not limited to these.

It is preferable that it is a compound which shows a nematic liquid crystal phase in 50-150 degreeC in the process of removing the said solvent, although the liquid crystal compound in this invention dissolves in a solvent to make a solution, and apply | coats on a support body. The range which shows the nematic liquid crystal phase of a liquid crystal compound does not need to be 50-150 degreeC, It will not limit, if it is a compound which shows a nematic liquid crystal in the temperature range of 50-150 degreeC.

[Orientation order diagram]

The orientation order in the present invention (hereinafter sometimes referred to as S) is used as the use of the orientation of the polymer film and the degree of liquid crystal orientation, and is defined in the range of 0 ≦ S ≦ 1. S = 0 indicates a completely random state such as a liquid state. S = 1 indicates a state in which there is no fluctuation of molecules like crystals and is completely oriented in one direction. Generally, although it measures by the X-ray-diffraction pattern in order to measure the orientation order of a crystalline polymer film, when measuring the film which has nematic liquid crystallinity, in this method, since a sensitivity is bad, it is not preferable as a measuring method. As for the orientation order in this specification, "Nanofinder" measurement conditions manufactured by Tokyo Instruments Co., Ltd. were measured by attaching a polarization resolver in front of the spectroscope with an excitation laser wavelength of 532 nm and an excitation laser output of about 400 uW at the sample portion. The measuring method cut the film obliquely at about 1-2 degrees, and performed the polarization Raman measurement of the surface or interface vicinity in the liquid crystal material layer in a film. By rotating the film, the angle between the orientation of the film plane and the direction of the electric field of the incident laser polarization is changed and measured at several angles, and the polarization component I perpendicular to the incident laser polarization electric field among the scattered light components Spectroscopic detection was carried out using an analyzer. Moreover, about the band | band with the peak derived from the skeleton of a liquid crystalline compound, the fitting analysis based on the least square method was performed by the equation derived theoretically, and the orientation order diagram was obtained. .

When the optically anisotropic layer exhibits nematic liquid crystallinity, the orientation order of the present invention is preferably 0.3 ≦ S ≦ 0.7, more preferably 0.45 ≦ S ≦ 0.65. When the orientation order is in this range, it contributes to the improvement of the front contrast when the optically anisotropic layer is bonded to the liquid crystal display device. When the optically anisotropic layer exhibits smectic liquid crystallinity, it is preferable that it is 0.5 ≦ S ≦ 0.90, and more preferably 0.65 ≦ S ≦ 0.90.

[Alignment Film]

About the kind of the specific polymer used for the oriented film in this invention, both the polymer which can be crosslinked by itself, and the polymer which is bridge | crosslinked by a crosslinking agent can be used. Moreover, the combination of these can also be used. As an example of the polymer used for the oriented film in this invention, the compound of Paragraph No. of Unexamined-Japanese-Patent No. 8-338913 is mentioned, for example. Preferably water-soluble polymers (for example, poly (N- methylol acrylamide), carboxymethyl cellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol), among them gelatin, polyvinyl alcohol and modified poly Vinyl alcohol is more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are more preferable.

70-100% is preferable, as for the saponification degree of polyvinyl alcohol, 80-100% is more preferable, and 85-95% is further more preferable. It is preferable that the polymerization degree of polyvinyl alcohol is 100-3000.

The modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of the modified group include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, hydrocarbon groups substituted with fluorine atoms, thioether groups and polymerization. The group (unsaturated polymerizable group, epoxy group, aziridinyl group, etc.), an alkoxy silyl group (trialkoxy, dialkoxy, monoalkoxy), etc. are mentioned. As a specific example of these modified polyvinyl alcohol compounds, Paragraph No. 2000-56310 of Unexamined-Japanese-Patent No. 2000-0, Paragraph No. 2000-155216 of Paragraph No. 0022-Paragraph No. 2002-62426, for example The thing described in numbers [0018]-[0022], etc. are mentioned.

[Polymer A]

In this invention, it is preferable to contain the polymer (Hereinafter called polymer A) containing the repeating unit represented by following General formula (1), and it is derived from the repeating unit and fluoro aliphatic group containing monomer represented by following General formula (1). It is more preferable to contain the polymer containing the repeating unit of. Polymer A mainly contributes to the vertical alignment of the molecules of the liquid crystalline compound at the air interface of the optically anisotropic layer.

 General formula (1)

(In General Formula (1), R ¹ , R ² and R ³ each represent a hydrogen atom or a substituent. L is a combination of two or more selected from the following divalent linking groups selected from the following linking group or the following linking group. The divalent linking group formed by this is shown.

(Connector group)

Single bond, -O-, -CO-, -NR ^4- (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), -S-, -SO _2- , -P (= O) (OR ⁵ )-(R ⁵ represents an alkyl group, an aryl group or an aralkyl group), an alkylene group and an arylene group

Q represents a carboxyl group (-COOH) or a salt thereof, a sulfo group (-SO ₃ H) or a salt thereof, or a phosphonoxy {-OP (= 0) (OH) ₂ } or a salt thereof.)

In general formula (1), R <^1> , R <^2> and R <^3> , Preferably represent a substituent selected from a hydrogen atom or the following substituent groups, respectively.

(Substituent group)

Alkyl group (preferably C1-C20, More preferably, it is C1-C12, More preferably, it is a C1-C8 alkyl group, For example, a methyl group, an ethyl group, isopropyl group, tert- butyl group, n- Octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc. can be mentioned), alkenyl group (preferably C2-C20, More preferably, C2-C20) 12, More preferably, it is a C2-C8 alkenyl group, For example, a vinyl group, an aryl group, 2-butenyl group, 3-pentenyl group, etc. are mentioned, Alkynyl group (preferably C2-C8) 20, More preferably, it is a C2-C12, More preferably, it is an alkynyl group of C2-C8, For example, a propargyl group, 3-pentynyl group, etc. are mentioned, An aryl group (preferably carbon number) 6-30, more preferably an aryl group having 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms For example, a phenyl group, p-methylphenyl group, a naphthyl group, etc. are mentioned, Aralkyl group (preferably C7-30, More preferably, C7-20, More preferably, it is C7-12 It is an aralkyl group, For example, a benzyl group, a phenethyl group, 3-phenylpropyl group, etc. are mentioned, A substituted or unsubstituted amino group (preferably C0-20, More preferably, C0-10, More Preferably it is a C0-C6 amino group, For example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anilino group, etc. are mentioned),

Alkoxy group (preferably C1-C20, More preferably, it is C1-C16, More preferably, it is a C1-C10 alkoxy group, For example, a methoxy group, an ethoxy group, butoxy group etc. are mentioned. ), 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, for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc. may be mentioned. ) And an acyloxy 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, for example, an acetoxy group, a benzoyloxy group, and the like. 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, and examples thereof include an acetylamino group and a benzoylamino group). Can be used), Alkoxycarbonylamino group (Preferably, it is a C2-C20, More preferably, it is a C2-C16, More preferably, it is an C2-C12 alkoxycarbonylamino group, For example, a methoxycarbonylamino group etc. are mentioned. Aryloxycarbonylamino 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, for example, phenyloxycarbonyl An amino group, etc.), a sulfonylamino group (preferably a C1-C20, more preferably a C1-C16, still more preferably a C1-C12 sulfonylamino group, for example, methanesulfonyl Amino groups, benzenesulfonylamino groups, etc.), sulfamoyl groups (preferably carbon 0-20, more preferably 0-16 carbon atoms, still more preferably 0-12 carbon atoms) For example, sulfamoyl group, methyl sulfamoyl group, dimethyl sulfamoyl group, phenyl sulfamoyl group, etc. can be mentioned, carbamoyl group (preferably C1-C20, More preferably, it is C1-C20) 16, more preferably a carbamoyl group having 1 to 12 carbon atoms, for example, an unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc.);

Alkylthio group (preferably C1-C20, More preferably, it is C1-C16, More preferably, it is C1-C12 alkylthio group, For example, a methylthio group, an ethyl thio group, etc. are mentioned. Arylthio group (preferably an arylthio 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 phenylthio group and the like. ), Sulfonyl group (preferably a sulfonyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, and examples thereof include a methyl group and a tosyl group); Sulfinyl (preferably a sulfinyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group, a benzenesulfinyl group, and the like) , Ureido groups (preferably having 1 to 20 carbon atoms, more preferably Crab is a C1-C16, More preferably, a C1-C12 ureido group, For example, an unsubstituted ureido group, a methyl ureido group, a phenyl ureido group, etc. are mentioned, The phosphate amide group (preferably It is a C1-C20, More preferably, it is a C1-C12 phosphate amide group, For example, a diethyl phosphate amide group, a phenyl phosphate amide group, etc. are mentioned), A hydroxyl group , Mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, already A no group and a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, and the like, for example , Imidazolyl, flutes Group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, More preferably, it is a C3-C30, More preferably, it is a C3-C24 silyl group, For example, a trimethylsilyl group, a triphenyl silyl group, etc. are mentioned. These substituents may be further substituted by these substituents. Moreover, when it has two or more substituents, it may be same or different. Moreover, if possible, they may combine with each other and form the ring.

R ¹ , R ² and R ³ are each preferably a group represented by a hydrogen atom, an alkyl group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or -LQ described later, and a hydrogen atom, It is more preferable that it is a group represented by a C1-C6 alkyl group, a chlorine atom, and -LQ, It is still more preferable that it is a hydrogen atom, a C1-C4 alkyl group, It is especially preferable that it is a hydrogen atom, a C1-C2 alkyl group, R ² and R ³ are hydrogen atoms, R ¹ It is most preferable that it is this hydrogen atom or a methyl group. As a specific example of this alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, etc. are mentioned. This alkyl group may have a suitable substituent. Examples of the substituent include 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, sulfonamide group, sulforyl group, carboxyl group and the like. In addition, carbon number of an alkyl group does not contain the carbon atom of a substituent. The same applies to the carbon number of other groups below.

L represents a divalent linking group selected from the linking group, or a divalent linking group formed by combining two or more thereof. R ⁴ of —NR ⁴ — represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group in the linking group, and preferably a hydrogen atom or an alkyl group. In addition, R ⁵ of —PO (OR ⁵ ) — represents an alkyl group, an aryl group, or an aralkyl group, and is preferably an alkyl group. R ⁴ and R ⁵ When C represents an alkyl group, an aryl group, or an aralkyl group, carbon number is the same as that described in the "substituent group". L preferably contains a single bond, -O-, -CO-, -NR ^4- , -S-, -SO _2- , an alkylene group or an arylene group, and is preferably a single bond, -CO-, -O-, -NR ⁴ - is more preferable to contain a group, alkylene group or arylene group, and more preferably a single bond. When L contains an alkylene group, carbon number of an alkylene group becomes like this. Preferably it is 1-10, More preferably, it is 1-8, More preferably, it is 1-6. As a specific example of especially preferable alkylene group, a methylene group, ethylene group, trimethylene group, tetrabutylene group, hexamethylene group, etc. are mentioned. When L contains an arylene group, carbon number of an arylene group becomes like this. Preferably it is 6-24, More preferably, it is 6-18, More preferably, it is 6-12. As a specific example of an especially preferable arylene group, a phenylene group, a naphthalene group, etc. are mentioned. 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, particularly preferably Is 7-16. As a specific example of an especially preferable aralkylene group, a phenylene methylene group, a phenylene ethylene group, a methylene phenylene group, etc. are mentioned. The group mentioned as L may have a suitable substituent. Such substituents include those similar to the substituent groups as the substituent any of the above R ¹ ~R ^3.

Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

In the general formula (1), Q is a carboxyl group, a salt of a carboxyl group (for example, lithium salt, sodium salt, potassium salt, ammonium salt (for example, ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, Tetrabutylammonium, trimethylbenzylammonium, dimethylphenylammonium, etc.), pyridinium salts, etc.), sulfo groups, salts of sulfo groups (examples of cations forming salts are the same as those described in the above carboxyl groups), phosphonoxy groups, phosphonoxy Salt of the period (an example of a cation forming a salt is the same as that described in the above carboxyl group). More preferably, they are a carboxyl group, a sulfo group, and a phospho group, More preferably, they are a carboxyl group or a sulfo group, The most preferable is a carboxyl group.

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

The said polymer A may contain 1 type of repeating units represented by the said General formula (1), and may contain 2 or more types. Moreover, the said polymer A may have 1 type, or 2 or more types of repeating units derived from the said fluoro aliphatic group containing monomer. Preferably, it is preferable to contain the fluoro aliphatic group containing monomer described by General formula [1] of Unexamined-Japanese-Patent No. 2004-333852. In addition, the said polymer A may contain the other repeating unit of that excepting the above. There is no restriction | limiting in particular about said other repeating unit, The repeating unit guide | induced from the monomer which can be normal radical polymerization reaction is mentioned as a preferable example. It is preferable that the said polymer A contains 1 type, or 2 or more types of repeating units derived from the monomer chosen preferably from the monomer group of Unexamined-Japanese-Patent No. 2004-46038. .

Moreover, it is also preferable that the said polymer A contains the repeating unit derived from the monomer represented by General formula [2] described in Unexamined-Japanese-Patent No. 2004-333852.

It is preferable that the quantity of the fluoro aliphatic group containing monomer of the said polymer A is 5 mass% or more of the constituent monomer total amount of this polymer, It is more preferable that it is 10 mass% or more, It is further more preferable that it is 30 mass% or more. In the repeating unit derived from the fluoroaliphatic group-containing monomer, the amount of the repeating unit represented by the general formula (1) is 0.5% by mass or more of the total amount of the constituent monomers of the repeating unit derived from the fluoroaliphatic group-containing monomer. It is preferable that it is 1-20 mass%, It is more preferable that it is 1-10 mass%, It is most preferable that it is 1-5 mass%.

It is preferable that the mass mean molecular weight of the said polymer A used for this invention is 1,000,000 or less, It is more preferable that it is 500,000 or less, It is further more preferable that it is 5,000-50,000. Mass average molecular weight can be measured as a value of polystyrene (PS) conversion using gel permeation chromatography (GPC).

Although it does not specifically limit about the polymerization method employ | adopted when manufacturing the said polymer A, It is preferable to use the method as described in Unexamined-Japanese-Patent No. 2004-46038.

It is also preferable that the polymer A has a polymerizable group as a substituent in order to fix the alignment state of the discotic liquid crystalline compound or rod-like liquid crystalline compound.

Although the specific example used suitably for this invention as said polymer A is shown below, this invention is not limited at all by these specific examples. Herein, the numerical values (a, b, c, d, etc.) in the formulas are mass percentages indicating the composition ratios of the respective monomers, and Mw is TSK Gel GMHxL, TSK Gel G4000HxL, and TSK Gel G2000 HxL (all of Tosoh Co., Ltd.). It is the mass mean molecular weight shown by the solvent THF and polystyrene conversion by differential refractometer detection by the GPC analyzer which used the column of (trade name).

The said polymer A used for this invention can be manufactured by a well-known method as mentioned above. For example, it can manufacture by adding and polymerizing a general purpose radical polymerization initiator in the organic solvent containing the monomer which has a fluoro aliphatic group, the monomer which has a hydrogen bond group, etc. previously. In addition, it can be manufactured by the same method as the above by additionally adding another addition polymeric unsaturated compound as the case may be. Depending on the polymerizability of each monomer, the dropping polymerization method for polymerizing while dropping monomers and initiators into the reaction vessel is also effective to obtain a polymer having a uniform composition.

Although the preferable range of content of the said polymer A in the composition for optically anisotropic layer formation changes with the use, it is preferable that it is 0.005-8 mass% in a composition (composition removed the solvent in the case of coating liquid), and 0.01- It is more preferable that it is 5 mass%, and it is still more preferable that it is 0.05-1 mass%. It is more effective by setting the addition amount of the repeating unit derived from the fluoroaliphatic group-containing monomer to 0.005% by mass or more, and by 8% by mass or less, it is more effective in inhibiting sufficient drying of the coating film. There exists a tendency for the performance as an optical film (for example, uniformity of retardation etc.) to improve more.

[Onium salt]

It is preferable that the optically anisotropic layer in this invention contains at least 1 sort (s) of an onium salt. The onium salt contributes to the vertical alignment of the molecules of the rod-like liquid crystal compound at the alignment film interface side. Examples of the onium salt include ammonium salts containing nitrogen atoms, sulfonium salts containing sulfur atoms, phosphonium salts containing phosphorus atoms, and the like.

As said onium salt, Preferably it is a quaternary onium salt, More preferably, it is a quaternary ammonium salt.

Quaternary ammonium salts are generally tertiary amines (eg, trimethylamine, triethylamine, tributylamine, triethanolamine, N-methylpyrrolidine, N-methylpiperidine, N, N-dimethylpipepe Razine, triethylenediamine, N, N, N ', N'-tetramethylethylenediamine, etc.) or nitrogen-containing heterocycle (pyridine ring, picoline ring, 2,2'-bipyridyl ring, 4,4'-ratio) Pyridyl ring, 1,10-phenanthroline ring, quinoline ring, oxazole ring, thiazole ring, N-methylimidazole ring, pyrazine ring, tetrazole ring, etc. alkylation (Menschutkin Reaction), alkenylation, Obtained by alkynylation or arylation.

As quaternary ammonium salt, the quaternary ammonium salt which consists of nitrogen-containing heterocycles is preferable, Especially preferably, it is quaternary pyridinium salt.

More specifically, the quaternary ammonium salt is preferably selected from quaternary pyridinium salts represented by the following general formula (3a) or general formula (3b) described later.

General formula (3a)

In general formula (3a), R <^8> is substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group Represents a hydrogen bonding group, m represents an integer of 1 to 3, and X ⁻ represents an anion.

In General Formula (3a), the alkyl group represented by R ⁸ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. These may be linear, branched, or cyclic. Examples of these alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, n-octyl group, neopentyl group and cyclohexyl group , Adamantyl group and cyclopropyl group.

The following are mentioned as an example of a substituent of an alkyl group. Substituted or unsubstituted alkenyl groups (eg, vinyl groups) having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms); A substituted or unsubstituted alkynyl group (for example, an ethynyl group) having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms); C6-C10 substituted or unsubstituted aryl group (for example, a phenyl group and a naphthyl group); Halogen atoms (eg, F, Cl, Br, etc.); A substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) (for example, a methoxy group and an ethoxy group); Substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms (for example, phenoxy group, biphenyloxy group, p-methoxyphenoxy group); Substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) (eg, methylthio group, ethylthio group); C6-C10 substituted or unsubstituted arylthio group (for example, phenylthio group); A substituted or unsubstituted acyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (for example, an acetyl group and a propionyl group);

A substituted or unsubstituted alkylsulfonyl group or arylsulfonyl group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) (for example, methanesulfonyl group and p-toluenesulfonyl group); Substituted or unsubstituted acyloxy group (eg, acetoxy group, propionyloxy group) having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms); A substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (for example, methoxycarbonyl group and ethoxycarbonyl group); C7-C11 substituted or unsubstituted aryloxycarbonyl group (for example, naphthoxycarbonyl group); Unsubstituted amino group or substituted amino group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) (for example, methylamino group, dimethylamino group, diethylamino group, alinino group, methoxyphenylamino group, chlorophenylamino group, pyri) Dilamino group, methoxycarbonylamino group, n-butoxycarbonylamino group, phenoxycarbonylamino group, methylcarbamoylamino group, ethylthiocarbamoylamino group, phenylcarbamoylamino group, acetylamino group, ethylcarbonylamino group, Ethylthiocarbamoylamino group, cyclohexylcarbonylamino group, benzoylamino group, chloroacetylamino group, methylsulfonylamino group);

A substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) (for example, an unsubstituted carbamoyl group, methylcarbamoyl group, ethyl carbamoyl group, n-butylcarbamoyl group, tert) -Butyl carbamoyl group, dimethyl carbamoyl group, morpholino carbamoyl group, pyrrolidinocarbamoyl group); Unsubstituted sulfamoyl group or substituted sulfamoyl group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) (eg, methyl sulfamoyl group, phenyl sulfamoyl group); Cyano group; Nitro group; Carboxyl group; Hydroxyl group; Heterocyclic group (for example, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzoimidazole ring, indolenin ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, alcohol An olan ring, a furan ring, a thiophene ring, a pyrazole ring, a pyrrole ring, a Croman ring, a coumarin ring). As a substituent of an alkyl group, Especially preferably, they are an aryloxy group, an arylthio group, an arylsulfonyl group, and an aryloxycarbonyl group.

The alkenyl group represented by R ⁸ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, for example, a vinyl group, an allyl group, 1-propenyl group, 1, 3- butadienyl group, etc. are mentioned.

As a substituent of an alkenyl group, what was mentioned as a substituent of the said alkyl group can be illustrated, A preferable range is also the same.

The alkynyl group represented by R ⁸ is preferably a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms, for example, an ethynyl group or 2-propy Neal etc. are mentioned. It is preferable that the substituent of an alkynyl group was mentioned as a substituent of the said alkyl group.

The substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms is preferable, and the aralkyl group represented by R ⁸ is, for example, a benzyl group, methylbenzyl group, biphenylmethyl group, naphthylmethyl group, or the like. The substituent of an aralkyl group is mentioned as a substituent of the said alkyl group.

The aryl group represented by R ⁸ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a fluorenyl group. It is preferable that the substituent of an aryl group was mentioned as a substituent of the said alkyl group. Moreover, in addition to these, an alkyl group (for example, methyl group, an ethyl group, etc.), an alkynyl group, and benzoyl group are preferable.

The heterocyclic group represented by R ⁸ is preferably a 5-6 membered saturated or unsaturated heterocyclic ring composed of carbon atom, nitrogen atom, oxygen atom or sulfur atom. Examples of these heterocyclic groups include oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzoimidazole ring, indolenin ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, alcohol An olan ring, a furan ring, a thiophene ring, a pyrazole ring, a pyrrole ring, a croman ring, and a coumarin ring are mentioned. The heterocyclic group may be substituted, and what was mentioned as a substituent of the said alkyl group as a substituent in that case is preferable. As a heterocyclic group represented by R <^8> , a benzoxazole ring and a benzothiazole ring are especially preferable.

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

D represents a hydrogen bondable group. Hydrogen bonds are present between electrically negative atoms (eg, O, N, F, Cl) and hydrogen atoms covalently bonded to the same electrically negative atom. As a theoretical interpretation of hydrogen bonds, there are reports, for example, in H. Uneyama and K. Morokuma, Jounal of American Chemical Society, Vol. 99, pages 1316-1133, 1977. As a specific form of a hydrogen bond, for example, JN Islaes Archierier, Kondo Tamots, Hiroyuki Oshima Translation, Intermolecular Forces and Surface Forces, Marrow Hills, page 98 of 1991, FIG. have. Examples of specific hydrogen bonds include, for example, those described in G. R. Desiraju, angewante Chemistry International Edition English, Vol. 34, p. 2311, 1995.

Preferred hydrogen bonding groups include mercapto group, hydroxy group, amino group, carbonamide group, sulfonamide group, acid amide group, ureido group, carbamoyl group, carboxyl group, sulfo group, nitrogen-containing heterocyclic group (e.g., imida). Zolyl group, benzimidazolyl group, pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinate And a mid group, a phthalimide group, a maleimide group, a uracil group, a thiouracil group, a barbituric acid group, a hydantoin group, a maleic acid hydrazide group, a isatin group, and a uramil group. Further preferred hydrogen bonding groups include amino groups, carboxyamide groups, sulfonamide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups and pyridyl groups, and particularly preferably amino groups, carbamoyl groups and pyridyls. The group can be mentioned.

The anion represented by X ⁻ may be either an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, bromine ion, iodine ion, etc.), a sulfonate ion (eg, methanesulfonic acid ion, Trifluoromethanesulfonic acid ion, methylsulfate ion, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion Etc.), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picric acid ions, acetate ions, phosphate ions (for example, hexafluorophosphate ions), and hydroxyl ions.

X ⁻ is preferably a halogen anion, sulfonate ion, or hydroxyl ion. In addition, X <^-> does not need to be monovalent anion, and divalent or more anion may be sufficient, In this case, the ratio of cation and anion in the said compound does not need to be 1: 1 either, and is determined suitably.

M is preferably 1 in the general formula (3a). When m is two or more, each D may be same or different.

Next, General Formula (3b) will be described.

General formula (3b)

In formula (3b), R ⁹ and R ¹⁰ Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and X ⁻ represents an anion. Indicates.

The substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group or substituted or unsubstituted heterocyclic group represented by R ⁹ and R ¹⁰ , respectively, It is the same as group represented by R <^8> in the said General formula (3a), and its preferable range is also the same. X ^- is an anion represented by the general formula (3a), X ^- the same as the anion represented by, it is also the same preferable range. As described above, X ⁻ does not have to be a monovalent anion, and may be a divalent or higher anion. In this case, the ratio of the cation and anion in the compound does not need to be 1: 2, and is appropriately determined.

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

The content of the onium salt in the optically anisotropic layer varies depending on the kind thereof, but is preferably 0.01 to 10% by mass, and preferably 0.05 to 7% by mass, based on the content of the liquid crystal compound used in combination. It is more preferable, and it is still more preferable that it is 0.05-5 mass%. Although two or more types of onium salt may be used, in this case, it is preferable that the sum total of content of all types of onium salts used is the said range.

In the optically anisotropic layer in this invention, you may contain other additives other than a liquid crystalline compound, a polymer A, and a cellulose ester. Examples of other additives include plasticizers, surfactants, polymerizable monomers, polymers, and the like. It is preferable that these additives have compatibility with essential components, such as a liquid crystalline compound, and do not contribute to control of the inclination angle of a liquid crystalline compound, or do not inhibit orientation.

[Method for producing optically anisotropic layer]

The optical compensating sheet of the present invention applies a composition (usually a coating liquid) containing a liquid crystalline compound and other additives as desired, for example, to the surface of the support, preferably the surface of the alignment film, to form molecules of the liquid crystalline compound. It can produce by aligning and fixing this orientation state.

As a solvent used for preparation of a coating liquid, an organic solvent is preferable. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethylsulfoxide, heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene , Hexane), alkyl halides (e.g. chloroform, dichloromethane, tetrachloroethane), esters (e.g. methyl acetate, butyl acetate), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. For example, tetrahydrofuran, 1,2-dimethoxyethane) is preferable, and an alkyl halide and a ketone are preferable, In addition, you may use two or more types of organic solvent together. It is preferable that it is 25 mN / m or less, and, as for the surface tension of a coating liquid, it is more preferable that it is 22 mN / m or less.

Application of the coating liquid can be carried out by a known method (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method), wire bar coating method, die coating method Application by the method is preferable.

It is preferable to perform fixation by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is preferable. It is preferable to contain a polymeric monomer and a polymerization initiator which contribute to fixation of a liquid crystalline compound in a coating liquid. As the polymerizable monomer, for example, a compound having a vinyl group, vinyloxy group, acryloyl group and methacryloyl group is preferable. 1-50 mass% is preferable with respect to a liquid crystalline compound, and, as for the addition amount of the said compound, it is more preferable that it is 3-30 mass%. Moreover, when mixing and using the monomer whose polymerizable reactive functional group number is three or more, adhesiveness between an orientation film and an optically anisotropic layer can be improved, and it is more preferable.

Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2367661 and 2367670), acyloinether (described in US Pat. No. 2448828), α-hydrocarbon substituted aromatic acyl in compounds (US Pat. 2722512 specification), polynuclear quinone compounds (see US Pat. No. 3046127, pp. 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketones (described in US Pat. No. 3549367), acridine and Phenazine compounds (described in Japanese Unexamined Patent Publication No. 60-105667 and U.S. Patent 4239850) and oxadiazole compounds (described in U.S. Patent 4212970). It is preferable that it is 0.01-20 mass% with respect to solid content of a coating liquid, and, as for the usage-amount of a photoinitiator, it is more preferable that it is 0.5-5 mass%.

It is preferable to use an ultraviolet-ray for the light irradiation of the orientation fixation of a liquid crystalline compound (liquid crystalline molecule). It is preferable that irradiation energy exists in the range of 20mJ / cm <2> -50J / cm <2>, It is more preferable that it exists in the range of 20mJ / cm <2> -5000mJ / cm <2>, It is further more preferable that it exists in the range of 100mJ / cm <2> -800mJ / cm <2>. Moreover, you may irradiate light under heating conditions in order to accelerate photopolymerization reaction. In order to make Rth / d into 0.12 or more, it is preferable to set it as at least 100 degrees C or less, and, as for the temperature which carries out orientation fixation, it is more preferable to set it as 80 degrees C or less. Moreover, in order to maintain adhesiveness of a liquid crystal layer and a support body, it is preferable to harden at 40 degreeC or more.

It is preferable that the thickness of the optically anisotropic layer formed in this way is 0.1-20 micrometers, It is more preferable that it is 0.5-15 micrometers, It is further more preferable that it is 1-10 micrometers. Moreover, you may form a protective layer on an optically anisotropic layer.

[Support]

In this invention, you may form the said optically anisotropic layer on a support body. It is preferable that a support body is transparent, and specifically, it is preferable that light transmittance is 80% or more. It is preferable that the support has small wavelength dispersion, and specifically, the ratio of Re ₄₀₀ / Re ₇₀₀ is preferably less than 1.2. Especially, a polymer film is preferable. The support of the optically anisotropic layer may be part of a retardation film, or may be all of the retardation film. Moreover, the support body of the said optically anisotropic layer may function as a protective film (polarizing plate protective film) of the polarizing plate in this invention.

It is preferable that the optical anisotropy of a support body is small, It is preferable that in-plane retardation (Re) is 20 nm or less, It is more preferable that it is 10 nm or less, It is most preferable that it is 5 nm or less. In addition, when serving as a retardation film, it is preferable that Re is 20 nm-150 nm, It is more preferable that it is 40 nm-115 nm, It is further more preferable that it is 60 nm-95 nm. Moreover, Nz is 1.5-7, It is more preferable that it is 2.0-5.5, It is further more preferable that it is 2.5-5.0.

Examples of the polymer film serving as the support include films of cellulose esters, polycarbonates, polysulfones, polyethersulfones, polyacrylates, and polymethacrylates. A cellulose ester film is preferable and cellulose acetate is more preferable. It is preferable to form a polymer film by the solvent cast method. It is preferable that it is 20-500 micrometers, and, as for the thickness of a support body, it is more preferable that it is 40-200 micrometers. Surface treatment (e.g. glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment) on the support in order to improve the adhesion between the support and the layer (adhesive layer, vertical alignment layer or optically anisotropic layer) formed thereon You may carry out. An adhesive layer (undercoat layer) may be formed on the support. Moreover, even when a support body is a film, such as a polymer which has a polymeric group, since adhesiveness with an optically anisotropic layer improves, it is preferable. In addition, in order to provide sliding property in a conveyance process, or to prevent adhesion | attachment of the back surface and the surface after winding, the support body and the long support body are 5% of solid content weight ratio for inorganic particle whose average particle size is 10-100 nm. It is preferable to use what formed the polymer layer which mixed -40% by one side of a support body by application | coating and covalent edge with a support body.

The optical compensation sheet of the present invention can be used alone or in a member of a liquid crystal display device. The optical compensation sheet can be integrated with a polarizing plate and inserted into a liquid crystal display device as one member of the polarizing plate. The polarizing plate in which the optical compensation sheet of the present invention is integrated not only has a polarizing function but also contributes to the expansion of the viewing angle of the liquid crystal display device. Moreover, you may use the optical compensation sheet of this invention as a protective film of a polarizing film, and if it is set as such a structure, it contributes to thickness reduction of a liquid crystal display device.

Hereinafter, the polarizing plate using the optical compensation sheet of this invention is demonstrated in detail.

[Polarizing Plate]

The polarizing plate generally has a polarizing film produced by adsorbing and orienting a dichroic substance to a base film, and a protective film adhered to at least one side of the polarizing film. As a polymer used for the base film of a polarizing film, a polyvinyl alcohol (hereinafter PVA) type polymer is common. As the dichroic substance, iodine or a dichroic dye is used alone or in combination.

PVA used for a polarizing film here is what saponified polyvinyl acetate normally, For example, you may contain components copolymerizable with vinyl acetate, such as unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, and vinyl ether. . Moreover, modified PVA containing an acetacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, etc. can also be used. Although the saponification degree of PVA is not specifically limited, From a viewpoint of solubility, polarization property, heat resistance, moisture resistance, etc., 80-100 mol% is preferable and 90-100 mol% is especially preferable. Moreover, although the polymerization degree of PVA is not specifically limited, 1000-10000 are preferable and 1500-5000 are more preferable at film strength, heat resistance, moisture resistance, and stretchability. Moreover, it does not specifically limit about the syndiotactic of PVA, You can take arbitrary values according to the objective.

In the procedure for dyeing and stretching PVA to produce a polarizing film, a PVA film serving as a disk is stretched in a dry or wet manner and then immersed in a solution of iodine or a dichroic dye, or a PVA film in a solution of iodine or a dichroic dye. The method of extending | stretching and orientating, the method of extending | stretching and orienting by wet or dry after immersing a PVA film in iodine or a dichroic dye, etc. are mentioned. Moreover, when forming a PVA original film by the solution film forming method, the method of previously containing a dichroic substance in a PVA solution can also be employ | adopted.

The manufacturing method by wet drawing of a typical polarizing plate is described below. First, the raw PVA film is preliminarily swollen in an aqueous solution. Subsequently, it is immersed in the solution of dichroic substance, and a dichroic substance is adsorb | sucked. Moreover, it uniaxially stretches in an advancing direction in aqueous solution of boron compounds, such as a boric acid. As needed, you may form a color adjustment bath, a hardening bath, etc. later. When dried to some extent, a protective film is adhere | attached using adhesives, such as PVA. It can further dry and obtain a polarizing plate.

In the preliminary swelling liquid, you may add various organic solvents, an inorganic salt, a plasticizer, boric acids, etc. in aqueous solution.

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

As a drawing process of PVA, tension is applied to the width direction of a film by extending | stretching means, such as a tenter system, in addition to the method of providing tension in the advancing direction of a continuous film, extending | stretching and orienting a film in a advancing direction as illustrated above. The method of providing and orientating in the width direction can also be applied. It is preferable to perform extending | stretching 3 times or more in 1-axis direction, and 4.5 times or more is more preferable. You may perform biaxial stretching according to the purpose of use of a polarizing film. Although the film thickness after extending | stretching is not specifically limited, From a viewpoint of handleability, durability, and economical efficiency, 5-100 micrometers is preferable and 10-40 micrometers is more preferable. Although the temperature at the time of extending | stretching changes with extending conditions, Preferably it is 10-250 degreeC. When dry-stretching at the temperature of 100 degreeC or more, it is preferable to implement in inert gas atmosphere, such as nitrogen. Moreover, before dyeing the previously stretched film, it is preferable to perform a crystallization process at the temperature of 100 degreeC or more.

As a dyeing method, not only the dipping method illustrated above but arbitrary means, such as application | coating or spraying of an iodine or dye solution, are possible. Moreover, not only the liquid layer adsorption mentioned above but also the adsorption by donation can be performed as needed. It is also preferable to dye with a dichroic dye. As a specific example of a dichroic dye, pigments, such as an azo pigment, a stilbene pigment, a pyrazolone pigment, a triphenylmethane pigment, a quinoline pigment, an oxazine pigment, a thiazine pigment, and an anthraquinone pigment, for example A system compound is mentioned. Although water-soluble is preferable, it is not in this range. Moreover, it is preferable that hydrophilic substituents, such as a sulfonic acid group, an amino group, and a hydroxyl group, are introduce | transduced into these dichroic molecules.

Typical examples of dichroic molecules include CIDirect.Yellow.12, CIDirect.Orange.39, CIDirect.Orange.72, CIDirect.Red.28, CIDirect.Red.39, CIDirect.Red .79, CIDirect.Red.81, CIDirect.Red.83, CIDirect.Red.89, CIDirect.Violet.48, CIDirect.Blue.67, CIDirect.Blue.90, CIDirect.Green. 59, CIAcid. Red. 37, and the like. In addition, Japanese Unexamined Patent Publication No. Hei 1-61202, Japanese Unexamined Patent Publication No. Hei 1-72907, Japanese Unexamined Patent Publication No. Hei 1-72907, Japanese Patent Application Laid-Open No. Hei 1-183602, and Japanese Patent Application Laid-Open No. 2000-48105 And the dyes described in each of JP-A-2000-65205 and JP-A-7-261024. In particular, C.I.Direct.Red.28 (Congo red) has long been known to be suitable for this use. These dichroic molecules are used as free acids or as salts of alkali metal salts, ammonium salts and amines.

These dichroic molecules can produce polarizers having various colors by blending two or more kinds. It is preferable to mix | blend various dichroic molecules so that the compound (color) which shows black, or black may be exhibited when a polarizing axis orthogonally crosses a polarizing element as a polarizing element or a polarizing plate, and is excellent in both single-sheet transmittance and polarization ratio.

It is preferable to contain the additive which crosslinks to PVA in the manufacturing process of a polarizing film from a viewpoint of improving the heat resistance and moisture resistance of a polarizing film. As the crosslinking agent, those described in US Reissue Patent No. 232897 can be used, and boric acid and boron are preferably used practically. In addition, it is also known that the polarizing film contains metal salts such as zinc, cobalt, zirconium, iron, nickel, and manganese, which is known to increase durability. These crosslinking agents and metal salts may be contained in any of the preliminary swelling bath, dichroic substance dyeing bath, stretching speed, curing bath, color adjustment bath and the like described above, and the order of the steps is not particularly limited. There is no limitation in particular as an adhesive agent which bonds a protective film and a polarizing film, A well-known thing, such as a PVA system, a modified PVA system, a urethane system, an acryl type, can be used arbitrarily. 0.01-20 micrometers is preferable and, as for the thickness of an adhesive layer, 0.1-10 micrometers is more preferable.

As the polarizing plate of the present invention, the optical compensation sheet of the present invention is preferably adhered to one surface of the polarizing film (more preferably, the support surface of the optical compensating sheet having the support is in contact with the polarizing film), and on the opposite surface thereof. It is preferable to arrange | position the polymer film which consists of a cellulose acylate etc. (to make an arrangement of an optically anisotropic layer / polarizing film / polymer film).

The optical compensation sheet of the present invention can be used in various liquid crystal display devices. In particular, it is preferable to use it for the liquid crystal display device of an IPS mode. When the optical compensation sheet of this invention is arrange | positioned in the liquid crystal display device which has a liquid crystal cell and a pair of polarizing film which clamps this liquid crystal cell, it is arrange | positioned between at least one of the said pair of polarizing films and the said liquid crystal cell. desirable. It is preferable that the optical compensation sheet of this invention determines the optical characteristic of an optically anisotropic layer so that the liquid crystalline compound in a liquid crystal cell in black display of a liquid crystal display device may be compensated. Since the orientation state of the liquid crystal compound in the liquid crystal cell in black display changes with the mode of a liquid crystal display device, the preferable range of the optical characteristic of the said optically anisotropic layer also changes with a use. About the orientation state of the liquid crystal compound in a liquid crystal cell, it describes in P411-414 etc. of IDW'00, FMC7-2.

As described above, the optical properties of the optical compensation sheet of the present invention vary in a preferable range depending on the use thereof, for example, which mode is used for optical compensation of the liquid crystal cell. In the IPS mode liquid crystal display device, the Re of the optically anisotropic layer is preferably -5 to 5 nm, more preferably -3 to 3 nm, and Rth is preferably -80 to -400 nm, preferably -150 to It is more preferable that it is -350 nm. In order to form an optically anisotropic layer exhibiting such optical characteristics, for example, a rod-like liquid crystalline compound is used to vertically align (the orientation of the long axis of the rod-shaped molecules to be substantially perpendicular to the optically anisotropic layer plane) to form a vertical alignment. It is preferable to fix in a state. Moreover, it is preferable that it is 20-150 nm, and, as for Re of a support body, it is more preferable that it is 20-100 nm. It is preferable that Nz is 1.5-7.0, and it is more preferable that it is 2.0-6.0.

As for the liquid crystal display device in the IPS mode, details are disclosed in Japanese Patent Laid-Open No. 2003-207797, Japanese Patent Laid-Open No. 2005-128498 and the like, and the contents can be applied to the present invention.

Example

The features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, the amounts used, the ratios, the treatment contents, the treatment sequences, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the specific example shown below.

Comparative Example 1-1

(Production of IPS Mode Liquid Crystal Cell 1)

As shown in FIG. 1, the electrodes 2 and 3 were arrange | positioned on one glass substrate so that the distance between adjacent electrodes might be set to 20 micrometers, the polyimide film was formed as an orientation film on it, and the rubbing process was performed. The rubbing process was performed to the direction 4 shown in drawing. A polyimide film was formed on one surface of one glass substrate prepared separately, the rubbing process was performed, and it was set as the orientation film. The two glass substrates are opposed to each other so that the alignment films face each other, the substrate has a gap (gap) d of 3.9 µm, the rubbing directions of the two glass substrates are parallel to each other, and the refractive index anisotropy (Δn) is 0.0769 and the dielectric constant. The nematic liquid crystalline compound whose anisotropy (Δε) is positive 4.5 was sealed. The value of d · Δn of the liquid crystal layer was 380 nm. In Fig. 1, reference numeral 1 denotes a liquid crystal element pixel region, 2 denotes a pixel electrode, 3 denotes a display electrode, 4 denotes a rubbing direction, 5a and 5b denote directors of the liquid crystal compound during black display, and 6a denotes 6b. The director of the liquid crystal compound at the time of white display is shown, respectively.

(Production of Polymer Base Material (Support))

The following composition was put into the mixing tank, it stirred while heating, and each component was dissolved and the cellulose acetate solution was prepared. The solution was filtered using a filter paper (Advantech, No. 63) having a retention particle size of 4 µm and a filtrate time of 35 seconds at 0.5 MPa (5 kg / cm 2) or less.

 Cellulose Acetate Solution Composition  100% by mass of cellulose acetate (polymerization degree 300, mN / mw = 1.5) of acetation degree 60.9% by weight of triphenylphosphate (plasticizer) 7.8 parts by mass of biphenyldiphenylphosphate (plasticizer) 3.9 parts by mass of methylene chloride (first solvent) Methanol (second solvent) 54 parts by mass 1-butanol (third solvent) 11 parts by mass

In another mixing tank, 16 parts by mass of the following retardation increasing agent A, 8 parts by mass of the retardation increasing agent B, 0.28 parts by mass of silicon dioxide fine particles (average particle size: 100 nm), 80 parts by mass of methylene chloride, and methanol 20 A mass part was charged and stirred while heating to prepare solution A. 40 mass parts of this solution A were mixed with 474 mass parts of cellulose acetate solutions, and it fully stirred, and doping was prepared.

Retardation Synergist A

 Retardation Synergist B

The obtained doping was cast using a band softener. The film having a residual solvent amount of 15% by mass was transversely stretched at a stretching ratio of 20% using a tenter under a condition of 130 ° C, held at 50 ° C for 30 seconds as the width after stretching, and then the clip was removed to obtain a cellulose acetate film. Produced. The amount of residual solvent at the time of completion | finish of extending | stretching was 5 mass%, It further dried, and made the film into the amount of residual solvent less than 0.1 mass%.

Thus, the thickness of the obtained polymer base material was 80 micrometers. About the produced polymer base material, the light-incidence angle dependency of Re was measured using the automatic birefringence meter (KOBRA-21ADH, the product made by Oji Measurement Instruments Co., Ltd.). It was found that Re was 60 nm and Rth was 200 nm, and from this, nz was 3.8.

(Production of optical compensation sheet)

The saponification process of the produced polymer base material surface was performed, and on this film, the orientation film formation coating liquid of the following composition was adjusted with potassium hydroxide so that it might be set to pH 6.0. 20 ml / m <2> of the said alignment film application liquid was apply | coated with the wire bar coater. It dried for 60 second in the warm air of 60 degreeC, and 120 second in the warm air of 100 degreeC, and obtained the oriented film.

(Composition of Orientation Film-Forming Coating Liquid)

20 parts by mass of the following modified polyvinyl alcohol

0.05 parts by mass of potassium hydroxide

Glutalaldehyde 0.5 parts by mass

360 parts by weight of water

120 parts by mass of methanol

(Formation of Optically Anisotropic Layer)

First, the optically anisotropic layer formation solution which melt | dissolved the following composition in 102 g of methyl ethyl ketone was prepared.

(The composition of the optically anisotropic layer)

Having two acrylate groups

45.07 mass parts of rod-like liquid crystalline compounds (Ac-2)

0.45 parts by mass of the following onium salt (1)

0.18 parts by mass of polymer A (exemplified compound P-15)

1.35 parts by mass of a photopolymerization initiator (irgacure 907, manufactured by Chiba Co., Ltd.)

Sensitizer (Kayacure DETX, Nippon Gunpowder Co., Ltd.) 0.45 parts by mass

Compound Ac-2

Onium salts (1)

This coating liquid was apply | coated to the surface of the said oriented film by the wire bar, respectively. This was affixed to the rim of a metal and heated for 1.5 minutes in a 70 degreeC thermostat, and the rod-shaped liquid crystalline compound was orientated. Next, UV irradiation was carried out at 60 ° C. with a 120 W / cm high-pressure mercury lamp for 20 seconds to crosslink the rod-like liquid crystalline compound, and then cooled to room temperature to prepare an optically anisotropic layer. Regarding the optically anisotropic layer thus produced, the optical incidence angle dependence of Re was measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Measurement Instruments Co., Ltd.). It was 260 nm. Moreover, the optically anisotropic layer showed homeotropic orientation. Rth / d was found to be 0.14.

(Evaluation of the orientation order of the optically anisotropic layer)

Using "Nanofinder" manufactured by Tokyo Instruments Co., Ltd., the orientation order diagram was calculated with reference to the method described on pages 651 to 654 of Proceedings of IDW'04, 651 (2004). The results are shown in Table 1.

(Measuring degree of polymerization of optically anisotropic layer)

The degree of polymerization of the optically anisotropic layer was measured using a 710 FT-IR SPECTROMETER manufactured by Nicolet. 810㎝ derived from an acrylate group ^- calculated from the peak area ratio of 1600㎝ ^-1 vicinity derived from a ^first group of peaks and esters, the composition of the residual acrylate group, followed by re-calculating the degree of polymerization of the optically anisotropic layer. The results are shown in Table 2.

(Evaluation of Adhesiveness of Optical Compensation Sheet)

The adhesiveness of the optical compensatory sheet was produced and evaluated according to the 8.5.2 checker scale tape method of JIS K 5400. However, Nitto Denko polyester adhesive tape NO31RH was used for evaluation. The results are shown in Table 2.

(Production of Low Re Cellulose Acetate)

The following composition was put into the mixing tank, it stirred while heating, and each component was melt | dissolved and the cellulose acetate solution A was prepared.

(Composition of Cellulose Acetate Solution A)

100 parts by mass of cellulose acetate having a degree of substitution of 2.86.

Triphenyl phosphate (plasticizer) 7.8 parts by mass

Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass

300 parts by mass of methylene chloride (first solvent)

54 parts by mass of methanol (second solvent)

11 parts by mass of 1-butanol

The following composition was put into the other mixing tank, it stirred while heating, each component was dissolved, and the additive solution B-1 was prepared.

(Composition of Additive Solution B-1)

80 parts by mass of methylene chloride

20 parts by mass of methanol

40 parts by mass of the following retardation lowering agent

Retardation lowering agents

40 mass parts of additive solution B-1 was added to 477 mass parts of cellulose acetate solution A, and it fully stirred, and doping was prepared. Doping was cast on drums cooled to 0 ° C. from dairy studies. The solvent content is removed outside of 70% by weight, and both ends in the width direction of the film are fixed with a pin tenter (pin tenter described in FIG. 3 of JP-A-4-1009), and the solvent content is 3 to 5% by mass. In the state, it dried, maintaining the space | interval which becomes an elongation of 3% of a horizontal direction (direction perpendicular | vertical to a machine direction). Thereafter, the rolls of the heat treatment apparatus were conveyed to further dry the resulting polarizing plate protective film (1; low Re cellulose acetate film) having a thickness of 80 µm.

When the optical characteristics were calculated by measuring the light incidence angle dependency of Re using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Instrument Co., Ltd.), Re was 1 nm and Rth was 3 nm. I could confirm it. Re (400) -Re (700) was 2 nm and Rth (400) -Rth (700) was 10 nm.

(Polarizing Plate Having Polarizing Film 1)

Next, iodine was adsorbed to the stretched polyvinyl alcohol film to prepare a polarizing film 1. A commercially available cellulose acetate film (Fujitech TD80UF, manufactured by Fuji Photo Film Co., Ltd., Re = 3 nm, Rth = 45 nm) was saponified for use in the protective film on the surface of the polarizing film 1. The saponification protective film formed the polarizing plate 1 with one side of the polarizing film 1 using the polyvinyl alcohol-type adhesive agent.

Using the polyvinyl alcohol-based adhesive for the polarizing plate 1, the optical compensation sheet produced as described above is used so that the polymer substrate (support) is the polarizing film side, and the transmission axis of the polarizing film 1 and the ground of the polymer substrate. The adhesion polarizing plate 1 was formed so that an axis might become vertical.

(Polarizing Plate Having Polarizing Film 2)

On the surface where the protective film of the polarizing plate 1 was not affixed, the low Re cellulose acetate film was attached using the polyvinyl alcohol-type adhesive agent, and the polarizing plate 2 was formed.

The polarizing plate 1 was attached to one of the IPS mode liquid crystal cells 1 so that the slow axis of the polymer substrate was parallel to the rubbing direction of the liquid crystal cell and the optically anisotropic layer was on the liquid crystal cell side.

Subsequently, the polarizing plate 2 is attached to the other side of the IPS mode liquid crystal cell 1 so that the protective film side of the polarizing plate 1 is the liquid crystal cell side, and the polarizing plate 1 is arranged so that cross nicol is arranged. A display device was manufactured. As a result of observing the obtained optical compensatory sheet, since the vertical alignment property of the optically anisotropic layer was maintained, even when viewed from the front and the direction inclined to 60 degrees from the normal line, orientation unevenness and orientation defect were not detected.

As shown in Table 1 below, liquid crystal display devices of Examples 1-A to 1-H were produced. In Examples 1-A, 1-B, 1-C, and 1-D, the polarizing film 2, the low Re cellulose acetate film, the liquid crystal layer, the optically anisotropic layer, the polymer substrate, The polarizing film 1 is laminated in order, and Example 1-E, 1-F, 1-G, and 1-H are each polarizing film 2, a polymer base material, an optically anisotropic layer, and a liquid crystal in order from a light source side, respectively. The layer, the low Re cellulose acetate film, and the polarizing film 1 were laminated in order.

About these, the front contrast and color change of the liquid crystal display device were measured using the measuring device (EZ-Contrast 160D, ELDIM make). In either case, front contrast and color change yielded good results.

Example No. 1-A 1-B 1-C 1-D 1-E 1-F 1-G 1-H Absorption axis of polarizing film 1 level level level level Absorption axis of polarizing film 1 level level level level Ground axis of polymer base Perpendicular level Perpendicular level Direction of Low Re Cellulose Acetate Film option option option option The direction of the film of the optically anisotropic layer option option option option Slow axis of liquid crystal layer Perpendicular Perpendicular level level Slow axis of liquid crystal layer Perpendicular Perpendicular level level The direction of the film of the optically anisotropic layer option option option option Low Re Cellulose Acetate Film Direction option option option option Polymer base slow axis Perpendicular level Perpendicular level Absorption axis of polarizing film 2 Perpendicular Perpendicular Perpendicular Perpendicular Absorption axis of polarizing film 2 Perpendicular Perpendicular Perpendicular Perpendicular Light source

 * "Horizontal" and "Vertical" respectively indicate the left and right directions and the up and down directions when the display is viewed from the front.

[Examples 1-2 to 1-4]

In Comparative Example 1-1, a polarizing plate was produced in the same manner as in Comparative Example 1-1 except that the addition amount of the compound containing one of the following acrylates (hereinafter referred to as compound Ac-1) was as in Table 2. And a liquid crystal display device were produced.

Compound Ac-1

[Comparative Example 2-1, Examples 2-2 to 2-4]

Except for changing the onium salt used in Comparative Example 1-1 and Examples 1-2 to 1-4 to the following onium salt (22), the same as in Comparative Example 1-1 and Examples 1-2 to 1-4, respectively To produce a polarizing plate, and produced a liquid crystal display device (shown as Comparative Example 2-1, Example 2-2, Example 2-3, and Example 2-4 in order). Since the vertical alignment property of the optically anisotropic layer was maintained, even when viewed from the front and the direction inclined to 60 degrees from the normal line, orientation unevenness and orientation defect were not detected.

Onium Salt (22)

[Comparative Example 3-1, Examples 3-2 to 3-4, Comparative Example 4-1, Examples 4-2 to 4-4]

Except having changed the amount of retardation increasing agent A or B, it carried out similarly to Comparative Example 1-1 and Examples 1-2-1-4, and produced eight types of optical compensation sheets (Comparative Example 3- in order). 1, Examples 3-2 to 3-4, Comparative Examples 4-1, and Examples 4-2 to 4-4). The Re light incidence angle dependency of the obtained optical compensation sheet was measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Meter Co., Ltd.).

In the optical compensation sheets obtained in Comparative Example 3-1 and Examples 3-2 to 3-4, Re was 54 nm and Rth was 175 nm (Nz = 3.5). In the optical compensation sheets obtained in Comparative Example 4-1 and Examples 4-2 to 4-4, Re was 55 nm and Rth was 200 nm (Nz = 4.1). These optical compensation sheets were produced in the same manner as in Comparative Example 1-1, respectively, and a liquid crystal display device was produced.

From the results of eight kinds of optical compensation sheets having different retardation values, even if Re and Rth of the support are changed, the vertical orientation (orientation order) tends to increase with the increase of the content of the liquid crystal compound having one acrylate group. It was confirmed.

[Comparative Example 5-1, Examples 5-2 to 5-4, Comparative Example 6-1, Examples 6-2 to 6-4, Comparative Example 7-1, Examples 7-2 to 7-4]

Except having changed the kind of rod-shaped liquid crystalline compound which has two acrylate groups contained in an optically anisotropic layer to the following compound (Ac-2-5), (Ac-2-6), (Ac-2-7) An optical compensation sheet was produced in the same manner as in Comparative Example 1-1 and Examples 1-2 to 1-4, and a liquid crystal display device was produced (Comparative Example 5-1, Examples 5-2 to 5-4, Comparative Examples 6-1, Examples 6-2 to 6-4, Comparative Examples 7-1, and Examples 7-2 to 7-4). Even if the kind of liquid crystalline compound changes, it was confirmed that the vertical orientation (orientation order) tends to increase with the increase of the content of the liquid crystalline compound having one acrylate group.

(Ac-2-5)

(Ac-2-6)

(Ac-2-7)

[Comparative Example 8-1, Examples 8-2 to 8-4, Comparative Example 9-1, Examples 9-2 to 9-4, Comparative Example 10-1, Examples 10-2 to 10-4,]

Except having made the kind of rod-shaped liquid crystalline compound which has one acrylate group contained in an optically anisotropic layer into the following compound (Ac-1-8), (Ac-1-9), (Ac-1-10) An optical compensatory sheet was produced in the same manner as in Comparative Example 1-1, and a liquid crystal display device was produced.

(Ac-1-8)

(Ac-1-9)

(Ac-1-10)

[Example 1-5, Comparative Example 1-6]

In Comparative Example 1-1, the liquid crystal compound having two acrylate groups and the liquid crystal compound having one acrylate group were changed as shown in Table 3, respectively, and the other one was carried out in the same manner.

[Example 8-5, Comparative Example 8-6]

In Comparative Example 1-1, the liquid crystal compound having two acrylate groups and the liquid crystal compound having one acrylate group were changed as shown in Table 3, respectively, and the other one was carried out in the same manner.

As can be seen from the above results, the orientation order increases by adding a liquid crystalline compound containing one acrylate group in one molecule to a liquid crystalline compound containing two acrylate groups in one molecule. The fluctuation of the liquid crystal became small and the contrast improved.

In addition, as apparent from the above table, the content (parts by weight) of the liquid crystal compound having two acrylate groups ≥ the content (parts by weight) of the liquid crystal compound having one acrylate group hardly affects the adhesion. However, it turned out that adhesiveness tends to deteriorate in content (weight part) of the liquid crystal compound which has two acrylate groups (weight part) <= content of the liquid crystal compound which has one acrylate group.

Example 11

Comparative Example 1-1 and Examples 1-2-1-4 except having adjusted the above-mentioned alignment film formation coating liquid with potassium hydroxide so that it may be set to pH 10.0, rubbing an alignment film, and removing the said onium salt (1) further. In the same manner as the above, a polarizing plate was produced, and a liquid crystal display device was manufactured. Since the optically anisotropic layer forms a hybrid orientation and orientation is maintained, even when viewed from the front and the direction inclined to 60 degrees from the normal, orientation unevenness and orientation defect were not detected. Moreover, even when a liquid crystal compound became hybrid orientation in a vertical alignment, it turned out that the orientation (orientation of order) tends to increase due to the increase in the content of the liquid crystal compound having one acrylate group.

Example 12

Comparative Example 1-1 and Examples 1-2-1-4 except having rubbed the alignment film, the said onium salt (1) and the polymer A (P-15) were further removed, and the following structural formula 12-A was added. In the same manner as the above, a polarizing plate was produced, and a liquid crystal display device was manufactured. Since the optically anisotropic layer forms homogeneous orientation and orientation is maintained, even when viewed from the front and the direction inclined from 60 to 60 degrees, orientation unevenness and orientation defect were not detected. Even when the liquid crystal compound was in homogeneous orientation, it was found that the orientation (orientation order) tends to increase due to the increase in the content of the liquid crystal compound having one acrylate group.

(12-A)

Example 13

The alignment film-forming coating liquid described above was adjusted with potassium hydroxide to pH 3.5, rubbing the alignment film, and further removing the onium salt (1) and polymer A (P-15), and having a cyclic chiral structure. Except having added the acryloyl compound, it carried out similarly to Comparative Example 1-1 and Examples 1-2-1-4, and produced the polarizing plate, and produced the liquid crystal display device. The optically anisotropic layer formed the cholesteric liquid crystal whose slow axis of a liquid crystalline compound is parallel on a transparent substrate. Since orientation was maintained, even when viewed from the front and the direction inclined to 60 degrees from the normal, orientation unevenness and orientation defect were not detected. Even when the liquid crystal compound became a cholesteric liquid crystal, it was found that the orientation (orientation order) tends to increase due to the increase in the content of the liquid crystal compound having one acrylate group.

Example 14

Example 1-2 except having changed the rod-like liquid crystalline compound which has two acrylate groups contained in an optically anisotropic layer into the rod-like liquid crystalline compound (Ac-14) which has four following acrylate groups. An optical compensation sheet was produced in the same manner as in 1-2, and a liquid crystal display device was produced. In this case, S (4) was 0.49, S (4, 2) was 0.53, P (4) was 99.2%, and P (4, 2) was 98.4%.

 (Ac-14)

Example 15

Example 1 except having changed the rod-shaped liquid crystalline compound which has two acrylate groups contained in an optically anisotropic layer into the rod-shaped liquid crystalline compound (Ac-14H) which has six following acrylate groups. The optical compensation sheet was produced like -2, and the liquid crystal display device was produced. In this case, the degree of orientation S (6) was 0.40 and S (6, 2) was 0.42, and P (6) was 98.6% and P (6,2) was 98.4%.

(Ac-14H)

The film thicknesses of the front retardation Re and the optically anisotropic layer of Example 14 and Example 15 were as Table 4 shown. When the number of acrylate groups was increased, the film thickness of the optically anisotropic layer changed in the direction of thickening. Although the thickness of an optically anisotropic layer should just be 10 micrometers or less, when the orientation of a liquid crystalline compound is considered, since it tends to become difficult to orientate when a film thickness becomes thick, it was suggested that the number of acrylate groups is more preferable to four.

Number of acrylate groups Re (nm) Film thickness (㎛) Example 14 4 200 2.4 Example 15 6 200 3.5

Example 16-1

In Example 1-2, as a method for forming the optically anisotropic layer described in Comparative Example 1-1, the method for forming the optically anisotropic layer was heated at 70 ° C and 90 seconds, and the orientation fixed temperature was changed to 80 ° C. Except having done, the optical compensation sheet was produced similarly. The obtained sample forms homeotropic orientation, and it turns out that a solvent remains and it becomes an optical compensation sheet without failure of planar shape by shrinkage of a polymer base material. Rth / d was 0.12, and it was confirmed that it became a sample with favorable adhesiveness.

Comparative Examples 15-1 to 2 and Examples 16-2 to 4

Except having changed the orientation fixing temperature into 30, 50, 70, 90, 110 degreeC, the optical compensation sheet was produced like Example 15, Rth / d, adhesiveness was evaluated, and it summarized in Table 3.

[Examples 15-3 to 4 and Examples 16-5 to 8]

The optical compensation was carried out in the same manner as in Example 16-1 except that the orientation fixing temperature was changed to 30, 50, 70, 90, and 110 ° C, and the polymerizable liquid crystal having two acrylate groups was changed to the following compound (Ac-15). A sheet was produced, Rth / d, adhesiveness was evaluated, and it summarized in Table 3.

(Ac-15)

Comparative Example 15-5

In Example 15, the optical compensation sheet was produced like Example 15 except having changed the heating temperature into 30 degreeC as the comparative example 1-1 for the formation method of an optically anisotropic layer. The sample obtained was unable to evaluate the sample because the solvent remained.

Comparative Example 15-6

In Example 15, the optical compensation sheet was produced like Example 15 except having changed the heating temperature to 190 degreeC as the comparative example 1-1 for the formation method of an optically anisotropic layer. The obtained sample had a poor surface shape as the polymer substrate shrinked, making it impossible to evaluate the sample.

In this invention, the orientation order of a liquid crystalline compound can be controlled by adding the liquid crystalline compound from which a polymeric group differs. In addition, by using the onium salt and the polymer A together, the optical compensation function is excellent, and when applied to an image display device, the front contrast is improved, and a novel optical compensation sheet having a wide viewing angle enlargement performance can be provided.

Claims (21)

An optical compensation sheet having at least two types of optically anisotropic layers containing a liquid crystalline compound having at least one polymerizable group in one molecule, and having a different number of polymerizable groups each of the liquid crystalline compounds. It has an optically anisotropic layer containing two types of liquid crystalline compounds (m and n are respectively positive integers and m> n each) in which the number of polymeric groups is m and n in at least 1 molecule, respectively, The orientation of the said optically anisotropic layer S (m, n)> S (m, n)> When the orientation order of the optically anisotropic layer which removed the liquid crystal compound whose number of polymerizable groups is n from this optically anisotropic layer is set to S (m), S (m, n)> S (m) optical compensation sheet. It has an optically anisotropic layer containing two types of liquid crystalline compounds (m and n are respectively positive integers and m> n each) in which the number of polymeric groups is m and n in at least 1 molecule, respectively, The polymerization degree of the said optically anisotropic layer When P (m, n) and the polymerization degree of the optically anisotropic layer which removed the liquid crystalline compound whose number of polymerizable groups are n from this optically anisotropic layer are set to P (m), it is P (m, n) <P (m) Optical compensation sheet. It has an optically anisotropic layer containing two types of liquid crystalline compounds (m and n are respectively positive integers and m> n each) in which the number of polymeric groups is m and n in at least 1 molecule, respectively, The orientation of the said optically anisotropic layer S (m, n) <S when ordering degree of order of the optically anisotropic layer which removed the liquid crystal compound whose number of polymerizable groups is n from S (m, n) and this optically anisotropic layer is set to S (m), (m) P (m, n) when the degree of polymerization of the optically anisotropic layer is P (m, n) and the degree of polymerization of the optically anisotropic layer from which the number of polymerizable groups is n is removed from the optically anisotropic layer is P (m). Optical compensation sheet which is <P (m). The method according to any one of claims 1 to 4, The optical compensation sheet whose polymerizable group which the said liquid crystalline compound has is an acrylate group and / or a methacrylate group. The method according to any one of claims 1 to 4, The optical compensation sheet whose number of polymeric groups which the said liquid crystalline compound has is an integer of 1-4. The method according to any one of claims 1 to 4, The optically anisotropic layer contains two types of liquid crystalline compounds in which the number of polymerizable groups included in the liquid crystalline compound is m and n (m and n are each positive integers and m> n), and the optically anisotropic layer When the mass parts of the liquid crystal compound to be contained are W (m) and W (n), the adhesion between the optically anisotropic layer and the support when satisfying W (m) ≥ W (n) is 6 or more in the test of JIS K 5400 standard. Optical compensation sheet. The method according to any one of claims 1 to 4, Furthermore, the optically anisotropic layer which has a support body, The said optically anisotropic layer is an optical compensation sheet in which the said liquid crystalline compound is orientated in any one of a homeotropic orientation, a homogeneous orientation, a hybrid orientation, a cholesteric liquid crystal orientation, and a uniaxial oblique orientation. The method according to any one of claims 1 to 4, Furthermore, the optical compensation sheet which has a support body, and the said liquid crystalline compound is a rod-like liquid crystalline compound, and this rod-shaped liquid crystalline compound is homeotropically oriented. The method according to any one of claims 1 to 4, The liquid crystal compound is aligned and fixed in the range of 40 to 100 ° C., and the optically anisotropic layer is 0.12 ≦ Rth / d ≦ 0.24 (where Rth is a retardation in the thickness direction of the optically anisotropic layer, and d is the film thickness of the liquid crystal compound). ) Optical compensation sheet. The method according to any one of claims 1 to 4, The optical compensation sheet containing the polymer in which the said optically anisotropic layer contains the repeating unit represented by following General formula (1). General formula (1) [Formula 1]

(In General formula (1), R <^1> , R <^2> and R <^3> represent a hydrogen atom or a substituent, respectively. L represents a divalent linking group selected from the following linking group or a divalent linking group formed by combining two or more selected from the following linking group. (Connector group) Single bond, -O-, -CO-, -NR ^4- (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), -S-, -SO _2- , -P (= O) (OR ⁵ )-(R ⁵ represents an alkyl group, an aryl group or an aralkyl group), an alkylene group and an arylene group Q represents a carboxyl group (-COOH) or a salt thereof, a sulfo group (-SO ₃ H) or a salt thereof, or a phosphonoxy {-OP (= 0) (OH) ₂ } or a salt thereof.) The method according to any one of claims 1 to 4, The optical compensation sheet in which the said optically anisotropic layer contains the polymer containing the repeating unit represented by following General formula (1), and the repeating unit derived from a fluoroaliphatic group containing monomer. General formula (1) [Formula 2]

(In General formula (1), R <^1> , R <^2> and R <^3> represent a hydrogen atom or a substituent, respectively. L represents a divalent linking group selected from the following linking group or a divalent linking group formed by combining two or more selected from the following linking group. (Connector group) Single bond, -O-, -CO-, -NR ^4- (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group), -S-, -SO _2- , -P (= O) (OR ⁵ )-(R ⁵ represents an alkyl group, an aryl group or an aralkyl group), an alkylene group and an arylene group Q represents a carboxyl group (-COOH) or a salt thereof, a sulfo group (-SO ₃ H) or a salt thereof, or a phosphonoxy {-OP (= 0) (OH) ₂ } or a salt thereof.) The method according to any one of claims 1 to 4, The optical compensation sheet, wherein the optically anisotropic layer contains at least one onium salt. The method according to any one of claims 1 to 4, Furthermore, it has a support body, Re is 20 nm-150 nm measured from the normal direction of the said support body, Rth of the said support body is 100 nm-300 nm, Re of the said optically anisotropic layer is 20 nm or less, The optical compensation sheet whose Rth of an optically anisotropic layer is -400 nm--80 nm. The polarizing plate which has the optical compensation film as described in any one of Claims 1-4, and a polarizing film. The polarizing plate which has at least the optical compensation sheet of Claim 14, a polarizing film, and is laminated in order of the said optically anisotropic layer, the said support body, and the said polarizing film, The slow-axis direction of the said support body and the direction of the absorption axis of the said polarizing film are substantially Polarizing plate orthogonal to the. The polarizing plate which has at least the optical compensation sheet of Claim 14, a polarizing film, and is laminated in order of the said optically anisotropic layer, the said support body, and the said polarizing film, The slow-axis direction of the said support body and the direction of the absorption axis of the said polarizing film are substantially Parallel to the polarizer. A liquid crystal cell having a pair of substrates and a liquid crystal layer in which the liquid crystal molecules sandwiched by the pair of substrates are oriented substantially parallel to the substrate at the time of black display, a first polarizing plate, and a second polarizing film, The said 1st polarizing plate is a polarizing plate of Claim 16, The first polarizing plate is formed so that the optically anisotropic layer side is the substrate side, and the long axis direction of the slow axis of the support and the liquid crystal molecules at the time of black display are substantially parallel to one outside of the pair of substrates. Arranged to be Moreover, the liquid crystal display device in which the said 2nd polarizing film is formed so as to mutually orthogonally cross with the absorption axis of the polarizing film of the said 1st polarizing plate on the other outer side of the said pair of board | substrates. It has a liquid crystal cell which has a pair of board | substrates and the liquid crystal layer clamped by this pair of board | substrate at the time of black display substantially parallel with respect to a board | substrate, a 1st polarizing plate, and a 2nd polarizing film, The said 1st polarizing plate is a polarizing plate of Claim 17, The first polarizing plate is formed so that the optically anisotropic layer side is the substrate side, and the long axis direction of the slow axis of the support and the liquid crystal molecules at the time of black display are substantially parallel to one outside of the pair of substrates. Is arranged to be Moreover, the liquid crystal display device in which the said 2nd polarizing film is formed so as to mutually orthogonally cross with the absorption axis of the polarizing film of the said 1st polarizing plate on the other outer side of the said pair of board | substrates. The method of claim 18 or 19, And a substantially isotropic adhesive layer and / or a substantially isotropic transparent protective film between the second polarizing film and the substrate. The method of claim 20, A liquid crystal display device wherein the transparent protective film is a cellulose acetate film satisfying the following formulas (I) and (II): (I): 0≤Re (630) ≤10 and Rth (630) │25 (II): Re (400) -Re (700) │≤10 and Rth (400) -Rth (700) │≤35 [Wherein Re (λ) is the front retardation value (unit: nm) at wavelength λ nm, and Rth (λ) is the retardation value (unit: nm) in the film thickness direction at wavelength λ nm.

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