JP2006091745A - Optical compensation sheet, elliptically polarizing plate, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical compensation sheet or the like to display an image of high display quality with no irregularity and little changes in the hue when the sheet or the like is applied to a large liquid crystal display. <P>SOLUTION: The optical compensation sheet has an optical anisotropic layer which contains at least one kind of fluoroaliphatic group-containing polymer containing a repeating unit derived from monomers expressed by general formula (1) and general formula (1-1) and a liquid crystal compound expressed by general formula (DI). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical compensation sheet having an optically anisotropic layer containing a liquid crystalline compound, a polarizing plate provided with the optical compensation sheet, and a liquid crystal display device.

Technical background

  Optical compensation sheets are used in various liquid crystal display devices in order to eliminate image coloring and expand the viewing angle. Conventionally, stretched birefringent films have been used as optical compensation sheets. In recent years, it has been proposed to use an optical compensation sheet having an optically anisotropic layer made of a discotic liquid crystalline compound on a transparent support instead of a stretched birefringent film. This optically anisotropic layer is usually formed by applying a composition containing a discotic liquid crystalline compound on an alignment film and heating the composition at a temperature higher than the alignment temperature to align the discotic liquid crystalline compound. It is formed by fixing. In general, the discotic liquid crystalline compound has a large birefringence and various alignment forms. By using a discotic liquid crystalline compound, it has become possible to realize optical properties that cannot be obtained with conventional stretched birefringent films.

  In each publication of Patent Document 1 and Patent Document 2, 2,3,6,7,10,11-hexa {4- is used as a discotic liquid crystalline molecule suitable for forming an optically anisotropic layer of a retardation plate. (6-Acryloyloxyhexyloxy) benzoyloxy} triphenylene is disclosed (Patent Documents 2 and 3). Incidentally, the retardation value (Δnd) of the retardation film is determined according to the optical properties of the liquid crystal cell to be compensated. The retardation value (Δnd) is the product of the refractive index anisotropy (Δn) of the optically anisotropic layer and the thickness (d) of the optically anisotropic layer. If the refractive index anisotropy (Δn) of the optically anisotropic layer is large, the liquid crystal cell can be compensated even if the thickness (d) of the layer is thin. However, it is very difficult to form an optically anisotropic layer having a sufficiently large refractive index anisotropy (Δn) with the discotic liquid crystalline compounds described in Patent Documents 4 and 5. (Patent Documents 3 and 4). Further, Patent Document 5 discloses a discotic liquid crystal having a large refractive index anisotropy, but the wavelength dispersion characteristic is deteriorated, that is, the wavelength dispersion is increased), and the performance improvement is insufficient. (Patent Document 5). In general, the wavelength dispersion characteristic and the refractive index anisotropy are in a trade-off relationship, and the wavelength dispersion characteristic deteriorates when the refractive index anisotropy is increased. This deterioration of the wavelength dispersion characteristic is not preferable because it deteriorates the color change in color display, which is one of the performances of the phase difference plate. For this reason, it has been desired to develop a technology that breaks away from the trade-off that the chromatic dispersion characteristics deteriorate when the refractive index anisotropy is increased.

  In the prior art, an optical compensation sheet has been developed mainly assuming a small or medium-sized liquid crystal display device of 15 inches or less. However, recently, it is also necessary to assume a liquid crystal display device having a large size of 17 inches or more and high brightness. When a conventional optical compensation sheet was attached as a protective film to a polarizing plate of a large liquid crystal display device, it was found that unevenness occurred on the panel. This defect is not so conspicuous in a small-sized or medium-sized liquid crystal display device, but it is necessary to further develop an optical compensation sheet that copes with light leakage unevenness in response to an increase in size and brightness.

  Further, in the prior art, the optical compensation sheet as described above is manufactured by applying and laminating a coating liquid on a web by a coater using a slot die, and recently, a desired function in the production of the optical compensation sheet. Therefore, there is an increasing demand for a coating method in a region of 20 μm or less, which is a thinner wet film thickness than in the past. Such an optical compensation sheet is required to have a precise coating film thickness accuracy and coating film properties, requires a highly accurate thin layer coating technique, and a technique for sharpening the tip lip of the slot die has been proposed ( Patent Document 6).

  On the other hand, the method using a wire bar as the coating method of the optical compensation sheet is likely to cause stepped unevenness due to the coating liquid vibration in the liquid receiving tank and the roll eccentricity and deflection related to coating. Further, since these coating methods are post-measuring methods, it is relatively difficult to ensure a stable film thickness. Therefore, in these coating methods, it is difficult to increase the coating speed beyond a certain speed, and the high productivity inherent in coating cannot be fully utilized.

JP-A-7-306317 Japanese Patent Laid-Open No. 9-104866 JP-A-7-306317 Japanese Patent Laid-Open No. 9-104866 JP 2001-166147 A Japanese National Publication No. 9-511682

  The present invention has been made to solve the above-described problems, and provides an optical compensation sheet for providing a phase difference plate that contributes to the expansion of the viewing angle and that has little change in the hue of a display image. In particular, even when applied to a large-sized liquid crystal display device, an optical compensation sheet that can contribute to the expansion of the viewing angle without causing unevenness and with little change in color of the displayed image.

（一般式（１）中、Ｒ¹¹は水素原子またはメチル基を表し、Ｘは酸素原子、イオウ原子または−Ｎ（Ｒ¹²）−を表し、Ｒ¹²は水素原子または炭素数１〜４のアルキル基を表す。Ｚは水素原子またはフッ素原子を表し、ｍは１〜６の整数を表し、ｎは２〜４の整数を表す。）
一般式（１−１）

（一般式（１−１）においてＡは下記の連結基群Ａから選ばれる２価（ｑ＝１）もしくは３価（ｑ＝２）の連結基、または、下記の連結基群Ａから選ばれる２つ以上を組み合わせて形成される２価（ｑ＝１）もしくは３価（ｑ＝２）の連結基を表し、また、連結基同士は酸素原子を介して結合してもよく、Ｚ¹は水素原子またはフッ素原子を表し、ｐは３〜８の整数、ｑは１または２を表す。）
（連結基群Ａ）
−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂−、−Ｃ₆Ｈ₄−および−Ｃ₆Ｈ₃＜（−Ｃ₆Ｈ₄−および−Ｃ₆Ｈ₃＜のベンゼン環上の置換位置は任意の位置でよい。）
一般式（ＤＩ）

（一般式（ＤＩ）中、Ｙ¹¹、Ｙ¹²およびＹ¹³は、それぞれ独立にメチンまたは窒素原子を表し、Ｌ¹、Ｌ²およびＬ³は、それぞれ独立に単結合または二価の連結基を表し、Ｈ¹、Ｈ²およびＨ³は、それぞれ独立に下記一般式（ＤＩ−Ａ）または下記一般式（ＤＩ−Ｂ）を表し、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に下記一般式（ＤＩ−Ｒ）を表す。）
一般式（ＤＩ−Ａ）

（一般式（ＤＩ−Ａ）中、ＹＡ¹およびＹＡ²は、それぞれ独立にメチンまたは窒素原子を表し、ＸＡは、酸素原子、硫黄原子、メチレンまたはイミノを表す。＊は上記一般式（ＤＩ）におけるＬ¹〜Ｌ³側と結合する位置を表し、＊＊は上記一般式（ＤＩ）におけるＲ¹〜Ｒ³側と結合する位置を表す。）
一般式（ＤＩ−Ｂ）

（一般式（ＤＩ−Ｂ）中、ＹＢ¹およびＹＢ²は、それぞれ独立にメチンまたは窒素原子を表し、ＸＢは、酸素原子、硫黄原子、メチレンまたはイミノを表す。＊は上記一般式（ＤＩ）におけるＬ¹〜Ｌ³側と結合する位置を表し、＊＊は上記一般式（ＤＩ）におけるＲ¹〜Ｒ³側と結合する位置を表す。）
一般式（ＤＩ−Ｒ）
＊−（−Ｌ²¹−Ｑ²）_n1−Ｌ²²−Ｌ²³−Ｑ¹
（一般式（ＤＩ−Ｒ）中、＊は一般式（ＤＩ）におけるＨ¹〜Ｈ³側と結合する位置を表し、Ｌ²¹は単結合または二価の連結基を表し、Ｑ²は少なくとも１種類の環状構造を有する二価の基を表し、ｎ１は０〜４の整数を表し、Ｌ²²は、＊＊−Ｏ−、＊＊−Ｏ−ＣＯ−、＊＊−ＣＯ−Ｏ−、＊＊−Ｏ−ＣＯ−Ｏ−、＊＊−Ｓ−、＊−Ｎ（Ｒ）−、＊＊−ＣＨ₂−、＊＊−ＣＨ＝ＣＨ−または＊＊−Ｃ≡Ｃ−を表し、＊＊はＱ²側と結合する位置を表し、Ｌ²³は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、Ｑ¹は重合性基または水素原子を表す。ｎ１が２以上のとき、複数個の−Ｌ²¹−Ｑ²は、それぞれ、同一でも異なっていてもよい。）
（２）前記一般式（ＤＩ）で表される液晶性化合物が下記一般式（ＤＩＩ）で表される、（１）に記載の光学補償シート。
一般式（ＤＩＩ）

（一般式（ＤＩＩ）中、Ｙ³¹、Ｙ³²およびＹ³³は、それぞれ独立にメチンまたは窒素原子を表し、Ｒ³¹、Ｒ³²およびＲ³³は、それぞれ独立に下記一般式（ＤＩＩ−Ｒ）を表す。）
一般式（ＤＩＩ−Ｒ）

（一般式（ＤＩＩ−Ｒ）中、Ａ³¹およびＡ³²は、それぞれ独立にメチンまたは窒素原子を表し、Ｘ³は、酸素原子、硫黄原子、メチレンまたはイミノを表し、Ｑ³¹は、６員環状構造を有する二価の連結基を表し、ｎ３は、１〜３の整数を表し、Ｌ³¹は＊−Ｏ−、＊−Ｏ−ＣＯ−、＊−ＣＯ−Ｏ−、＊−Ｏ−ＣＯ−Ｏ−、＊−Ｓ−、＊−Ｎ（Ｒ）−、＊−ＣＨ₂−、＊−ＣＨ＝ＣＨ−または＊−Ｃ≡Ｃ−を表し、＊はＱ³¹側と結合する位置を表し、Ｌ³²は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−ＮＨ−、−ＣＨ₂−、−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−ならびにこれらの組み合わせからなる群より選ばれる二価の連結基を表し、Ｑ³²は、重合性基または水素原子を表す。ｎ３が２以上のとき、それぞれのＱ³¹は同一でも異なっていてもよい。）
（３）前記一般式（１）で表されるモノマーから導かれる繰り返し単位を含むフルオロ脂肪族基含有ポリマーを含み、かつ、前記一般式（１）におけるＺが水素原子である、（１）または（２）に記載の光学補償シート。
（４）前記フルオロ脂肪族基含有ポリマーが、さらに、下記一般式（２）で表される繰り返し単位を含む重合体である、（１）〜（３）のいずれかに記載の光学補償シート。
一般式（２）

（一般式（２）中、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ、水素原子または置換基を表し、Ｌは単結合、−Ｏ−、−ＣＯ−、−ＮＲ²⁴−（Ｒ²⁴は水素原子、アルキル基、アリール基またはアラルキル基を表す）、−Ｓ−、−ＳＯ₂−、−Ｐ（＝Ｏ）（ＯＲ²⁵）−（Ｒ²⁵はアルキル基、アリール基またはアラルキル基を表す）、アルキレン基およびアリーレン基からなる群から選ばれる基１つ以上からなる２価の連結基を表し、Ｑは、無置換のカルボキシル基もしくはその塩、無置換のスルホ基もしくはその塩、または｛−ＯＰ（＝Ｏ）（ＯＨ）₂｝もしくはその塩、または、ポリ（アルキレンオキシ）基を含む基を表す。）
（５）前記光学異方性層中に、フルオロ脂肪族基含有ポリマーを少なくとも２種含有し、該フルオロ脂肪族基含有ポリマーの少なくとも１種は、一般式（１）または（１−１）で表されるモノマーから導かれる繰り返し単位を含むフルオロ脂肪族基含有ポリマーである、（１）〜（４）のいずれかに記載の光学補償シート。
（６）前記光学異方性層は、配向膜上に設けられており、該配向膜および／または光学異方性層は、スロットダイコート法により塗布してなる、（１）〜（５）のいずれかに記載の光学補償シート。
（７）少なくとも、偏光膜と、該偏光膜の片面に設けられた保護膜とを有し、該保護膜が、（１）〜（６）のいずれかに記載の光学補償シートである楕円偏光板。
（８）（７）に記載の楕円偏光板を有する、液晶表示装置。 The object of the present invention is achieved by the following optical compensation sheet, the following elliptically polarizing plate provided with the optical compensation sheet, and a liquid crystal display device composed thereof.
(1) At least one fluoroaliphatic group-containing polymer containing a repeating unit derived from a monomer represented by the following general formula (1) and general formula (1-1), and represented by the following general formula (DI) An optical compensation sheet having an optically anisotropic layer containing a liquid crystal compound.
General formula (1)

(In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Z represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, and n represents an integer of 2 to 4.)
General formula (1-1)

(In General Formula (1-1), A is selected from a divalent (q = 1) or trivalent (q = 2) linking group selected from the following linking group group A, or a linking group group A described below. represents a linking group of bivalent formed by combining two or more (q = 1) or trivalent (q = 2), also linking groups to each other may be bonded via an oxygen atom, Z ¹ is A hydrogen atom or a fluorine atom is represented, p is an integer of 3-8, q represents 1 or 2.)
(Linking group A)
_{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, - C 6 H 4 - and _{-C 6 H 3 <(- C} 6 H 4 - and -C ₆ H ₃ <benzene The substitution position on the ring may be any position.)
General formula (DI)

(In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom, and L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group. H ¹ , H ² and H ³ each independently represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² and R ³ each independently represent the following general formula Represents formula (DI-R).)
General formula (DI-A)

(In the general formula (DI-A), YA ¹ and YA ² each independently represents a methine or nitrogen atom, XA represents an oxygen atom, a sulfur atom, methylene or imino, and * represents the above general formula (DI). Represents the position of bonding to the L ^{1 to} L ³ side in **, and ** represents the position of bonding to the R ^{1 to} R ³ side in the general formula (DI).)
General formula (DI-B)

(In the general formula (DI-B), YB ¹ and YB ² each independently represent a methine or nitrogen atom, XB represents an oxygen atom, a sulfur atom, methylene or imino. * Represents the above general formula (DI) Represents the position of bonding to the L ^{1 to} L ³ side in **, and ** represents the position of bonding to the R ^{1 to} R ³ side in the general formula (DI).)
General formula (DI-R)
*-(-L ²¹ -Q ² ) _n1 -L ²² -L ²³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to the H ^{1 to} H ³ side in the general formula (DI), L ²¹ represents a single bond or a divalent linking group, and Q ² represents at least 1; N1 represents an integer of 0 to 4, L ²² represents **-O-, **-O-CO-, **-CO-O-, * * -O-CO-O -, ** - S -, * - N (R) -, ** - CH 2 -, ** - CH = CH- or ** - C≡C- represent, ** Represents a position bonded to the Q ² side, and L ²³ represents —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH— and —C≡C. -Represents a divalent linking group selected from the group consisting of these, and Q ¹ represents a polymerizable group or a hydrogen atom, and when n1 is 2 or more, a plurality of -L ²¹ -Q ² are each , Same or different Even if it is.)
(2) The optical compensation sheet according to (1), wherein the liquid crystalline compound represented by the general formula (DI) is represented by the following general formula (DII).
Formula (DII)

(In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or nitrogen atom, and R ³¹ , R ³² and R ³³ each independently represents the following general formula (DII-R) To express.)
General formula (DII-R)

(In the general formula (DII-R), A ³¹ and A ³² each independently represent a methine or nitrogen atom, X ³ represents an oxygen atom, a sulfur atom, methylene or imino, and Q ³¹ represents a 6-membered cyclic group. represents a divalent linking group having a structure, n3 represents an integer of 1 to 3, L ³¹ is * -O -, * - O- CO -, * - CO-O -, * - O-CO- O-, * -S-, * -N (R)-, * -CH _2- , * -CH = CH- or * -C≡C-, * represents a position bonded to the Q ³¹ side, L ³² is selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Represents a divalent linking group, and Q ³² represents a polymerizable group or a hydrogen atom. When n3 is 2 or more, each Q ³¹ may be the same or different.
(3) including a fluoroaliphatic group-containing polymer containing a repeating unit derived from the monomer represented by the general formula (1), and Z in the general formula (1) is a hydrogen atom (1) or The optical compensation sheet according to (2).
(4) The optical compensation sheet according to any one of (1) to (3), wherein the fluoroaliphatic group-containing polymer is a polymer further comprising a repeating unit represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ²¹ , R ²² and R ²³ each represent a hydrogen atom or a substituent, L is a single bond, —O—, —CO—, —NR ²⁴ — (R ²⁴ is hydrogen) An atom, an alkyl group, an aryl group or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ²⁵ ) — (R ²⁵ represents an alkyl group, an aryl group or an aralkyl group), Represents a divalent linking group consisting of one or more groups selected from the group consisting of an alkylene group and an arylene group, and Q represents an unsubstituted carboxyl group or a salt thereof, an unsubstituted sulfo group or a salt thereof, or {-OP (= O) (OH) ₂ } or a salt thereof, or a group containing a poly (alkyleneoxy) group.
(5) The optically anisotropic layer contains at least two fluoroaliphatic group-containing polymers, and at least one of the fluoroaliphatic group-containing polymers is represented by the general formula (1) or (1-1). The optical compensation sheet according to any one of (1) to (4), which is a fluoroaliphatic group-containing polymer containing a repeating unit derived from the represented monomer.
(6) The optically anisotropic layer is provided on an alignment film, and the alignment film and / or the optically anisotropic layer is applied by a slot die coating method, (1) to (5) The optical compensation sheet according to any one of the above.
(7) Elliptical polarized light having at least a polarizing film and a protective film provided on one surface of the polarizing film, wherein the protective film is the optical compensation sheet according to any one of (1) to (6) Board.
(8) A liquid crystal display device having the elliptically polarizing plate according to (7).

In the present invention, the optically anisotropic layer containing the fluoroaliphatic group-containing polymer represented by the general formula (1) and / or (1-1) and the liquid crystalline compound represented by the general formula (DI) Accordingly, the present invention provides an optical compensation sheet having a wide viewing angle expansion performance and an optical compensation sheet excellent in display quality without causing unevenness when applied to an image display device with little change in color of a display image. be able to. The optical compensation sheet of the present invention contributes to the improvement of viewing angle characteristics of various modes of liquid crystal display devices. In particular, even when applied to a large liquid crystal display device, it is possible to display an image with high display quality with little color change without causing unevenness.
Furthermore, by using a slot coater, particularly a slot coater having a slot die having a specific structure, a more preferable optical compensation sheet was obtained.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
The “polymer” in the present invention is intended to include a “copolymer”.

Hereinafter, a copolymer containing a repeating unit derived from at least one of the fluoroaliphatic group-containing monomers represented by the general formulas (1) and (1-1) according to the present invention (“fluorinated polymer” and Will be described in detail.
The fluoropolymer used in the present invention includes at least a repeating unit derived from at least one of the monomers represented by the general formulas (1) and (1-1), and preferably includes the general formulas (1) and (1 -1) a polymer (for example, acrylic resin, methacrylic resin) and / or a polymer containing a repeating unit derived from at least one monomer represented by formula (2) and containing a repeating unit represented by formula (2) A resin (for example, acrylic resin or methacrylic resin) in which a vinyl monomer copolymerizable with at least one of the monomers represented by the formulas (1) and (1-1) is polymerized is also preferable.

General formula (1)

In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, and X is preferably an oxygen atom. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z represents a hydrogen atom or a fluorine atom, preferably a hydrogen atom. m represents an integer of 1 to 6, preferably 1 or 2. n represents an integer of 2 to 4, preferably 3 or 4.
As for the compound represented by General formula (1), only 1 type may be used and 2 or more types of mixtures may be used.

（一般式（１−１）においてＡは下記の連結基群Ａから選ばれる２価（ｑ＝１）もしくは３価（ｑ＝２）の連結基、または、下記の連結基群Ａから選ばれる２つ以上を組み合わせて形成される２価（ｑ＝１）もしくは３価（ｑ＝２）の連結基を表し、また、連結基同士は酸素原子を介して結合してもよく、Ｚ¹は水素原子またはフッ素原子を表し、ｐは３〜８の整数、ｑは１または２を表す。）
（連結基群Ａ）
−ＣＨ₂−、−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂−、−Ｃ₆Ｈ₄−および−Ｃ₆Ｈ₃＜（−Ｃ₆Ｈ₄−および−Ｃ₆Ｈ₃＜のベンゼン環上の置換位置は任意の位置でよい。）
連結基群Ａ中、−Ｃ₆Ｈ₄−はフェニレン基を意味し、−Ｃ₆Ｈ₃＜は、ベンゼン環から３つの水素原子を取り去ってできる基を意図している。従って、「ベンゼン環上の置換位置は任意の位置でよい。」とは、−（ＣＦ₂）_p−Ｚ¹がベンゼン環上のいずれの位置で置換されていてもよいことを意図している。
一般式（１−１）で表される化合物は、１種類のみを用いてもよいし、２種類以上の混合物を用いてもよい。 General formula (1-1)

(In General Formula (1-1), A is selected from a divalent (q = 1) or trivalent (q = 2) linking group selected from the following linking group group A, or a linking group group A described below. represents a linking group of bivalent formed by combining two or more (q = 1) or trivalent (q = 2), also linking groups to each other may be bonded via an oxygen atom, Z ¹ is A hydrogen atom or a fluorine atom is represented, p is an integer of 3-8, q represents 1 or 2.)
(Linking group A)
_{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, - C 6 H 4 - and _{-C 6 H 3 <(- C} 6 H 4 - and -C ₆ H ₃ <benzene The substitution position on the ring may be any position.)
In the linking group group A, —C ₆ H ₄ — means a phenylene group, and —C ₆ H ₃ <means a group formed by removing three hydrogen atoms from the benzene ring. Therefore, “the substitution position on the benzene ring may be any position” means that — (CF ₂ ) _p —Z ¹ may be substituted at any position on the benzene ring. .
Only 1 type may be used for the compound represented by General formula (1-1), and 2 or more types of mixtures may be used for it.

  Specific examples of monomers that can be used in the production of the fluorine-based polymer that can be used in the present invention are listed below, but the present invention is not limited to the following specific examples. In addition, among the monomers constituting the exemplified compounds (P-1 to P-141) of the fluorine-based polymer described later, the monomers included in the general formula (1) or the general formula (1-1) are also fluorine-based compounds of the present invention. It is the meaning contained in the preferable specific example of a polymer.

  One of the fluoroaliphatic groups possessed by the fluoropolymer of the present invention is, for example, fluoro produced by an electrolytic fluorination method, a telomerization method (also called a telomer method) or an oligomerization method (also called an oligomer method). It is derived from an aliphatic compound. Regarding the production method of these fluoroaliphatic compounds, for example, “Synthesis and Function of Fluorine Compounds” (Supervision: Nobuo Ishikawa, Issue: CMC Co., 1987), “Chemistry of Organic Fluorines Compounds”. II "(Monograph 187, Ed by Milos Hudricky and Attila E. Pavlath, American Chemical Society 1995). The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1). showed that).

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

Next, the repeating unit represented by the general formula (2) will be described.
General formula (2)

In the general formula (2), R ²¹ , R ²² and R ²³ each represent a hydrogen atom or a substituent, and are preferably in the following order.
(1) A hydrogen atom or a substituent selected from the following substituent group T (2) A hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), Group represented by LQ (3) Hydrogen atom, alkyl group having 1 to 6 carbon atoms, chlorine atom, group represented by -LQ (4) Hydrogen atom, alkyl group having 1 to 4 carbon atoms ( 5) Hydrogen atom, alkyl group having 1 to 2 carbon atoms (6) R ²² and R ²³ are hydrogen atoms, R ²¹ is hydrogen atom or methyl group Specific examples of the alkyl group in the above are methyl group, ethyl group, Examples include n-propyl group, n-butyl group, sec-butyl group and the like. The alkyl group may have a suitable substituent. Examples of the substituent include a halogen atom, aryl group, heterocyclic group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxyl group, acyloxy group, amino group, alkoxycarbonyl group, acylamino group, oxycarbonyl Group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, sulfolyl group, carboxyl group and the like. The carbon number of the alkyl group does not include the carbon atom of the substituent. The same applies to the carbon number of other groups.

(Substituent group T)
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferably carbon numbers). 2 to 12, particularly preferably an alkynyl group having 2 to 8 carbon atoms, and examples thereof include a propargyl group and a 3-pentynyl group). A reel group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, and a naphthyl group. An aralkyl group (preferably an aralkyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, and a 3-phenylpropyl group. A substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms. Group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

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

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably an alkylthio group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is C6-C20, More preferably, it is C6-C16, Most preferably, it is C6-C12 arylthio group, for example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, particularly preferably a sulfonyl group having 1 to 12 carbon atoms, such as a mesyl group and a tosyl group, and a sulfinyl group (preferably having a carbon number of 1 to 20, more A sulfinyl group having 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms is preferable. Zensulfinyl group and the like), ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, an unsubstituted ureido group , Methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms). Yes, for example, diethyl phosphoric acid amide group, phenyl phosphoric acid amide group, etc.), hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, Carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1 to 0, more preferably a heterocyclic group of 1 to 12, for example, a heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group , Piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably A silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group). These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring (including a condensed ring).

L is selected from the group consisting of a single bond, —O—, —CO—, —NR ²⁴ —, —S—, —SO ₂ —, —P (═O) (OR ²⁵ ) —, an alkylene group and an arylene group. A divalent linking group consisting of one or more groups selected from the group consisting of a single bond, —O—, —CO—, —NR ²⁴ —, —S—, —SO ₂ —, an alkylene group and an arylene group. It is preferably a divalent linking group comprising one or more groups selected from one or more groups selected from the group consisting of a single bond, —CO—, —O—, —NR ²⁴ —, an alkylene group or an arylene group. The divalent linking group is more preferably a single bond.

In the linking group group, R ^{24 in} —NR ²⁴ — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom or an alkyl group. R ²⁵ in —PO (OR ²⁵ ) — represents an alkyl group, an aryl group or an aralkyl group, preferably an alkyl group. As the alkyl group, aryl group and aralkyl group for R ²⁴ and R ²⁵ , those exemplified in the above-mentioned Substituent group T are more preferable.
When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of particularly preferred alkylene groups include a methylene group, an ethylene group, a trimethylene group, a tetrabutylene group, and a hexamethylene group. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene groups and naphthalene groups. When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 34, more preferably 7 to 26, and particularly preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group. The group listed as L may have a suitable substituent. Examples of such a substituent include those similar to the substituent group T.
Specific examples of preferred L ¹ structures are shown below, but the present invention is not limited to these specific examples. In addition, the portion corresponding to L ¹ of the exemplified compounds (C-1 to C-25, A-1 to A-10) disclosed as specific examples of the monomer corresponding to the general formula (2) described later is also the present invention. It is intended to be included in the preferred specific structure of L ¹ . Poly (alkyleneoxy) is often a mixture of compounds having different degrees of polymerization X, and the degree of polymerization is expressed by an integer close to the average of the degrees of polymerization in the compounds shown as specific examples.

Q represents an unsubstituted carboxyl group or a salt thereof, an unsubstituted sulfo group or a salt thereof, {-OP (═O) (OH) ₂ } or a salt thereof, or a group containing a poly (alkyleneoxy) group. To express. Q is a carboxyl group, a salt of a carboxyl group (eg, lithium salt, sodium salt, potassium salt, ammonium salt (eg, unsubstituted ammonium salt, tetramethylammonium salt, trimethyl-2-hydroxyethylammonium salt, tetrabutylammonium salt, trimethyl) Benzylammonium salt, dimethylphenylammonium salt, etc.), pyridinium salt, etc.), sulfo group, sulfo group salt (examples of cations forming the salt are the same as those described above for carboxyl group), phosphonoxy group, phosphonoxy group salt (Examples of the cation forming the salt are the same as those described for the carboxyl group) or a group containing a poly (alkyleneoxy) group.
A poly (alkyleneoxy) group can be represented by (OR) _x , where R is an alkylene group having 2 to 4 carbon atoms, such as —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH. It is preferably (CH ₃ ) CH ₂ — or —CH (CH ₃ ) CH (CH ₃ ) —.
The oxyalkylene units in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), or two or more different oxyalkylenes may be randomly distributed. It may be a linear or branched oxypropylene or oxyethylene unit, or a linear or branched oxypropylene unit block and an oxyethylene unit block.
The poly (oxyalkylene) chain may include those linked by one or more linking groups (for example, -CONH-Ph-NHCO-, -S-, Ph represents a phenylene group). When the linking group has a valence of 3 or more, a branched oxyalkylene unit is obtained. Moreover, it is preferable that the terminal of polyoxyalkylene has a hydrogen atom and an alkyl group. As the alkyl group, a methyl group is preferable.
When a polymer containing a polymer unit having a poly (oxyalkylene) group is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.
Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials, such as trade name "Pluronic" (Pluronic (Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.) Known as "Carbowax (Glico-Products)", "Triton" (Toriton (Rohm and Haas)) and PEG (Daiichi Kogyo Seiyaku Co., Ltd.) It can manufacture by making it react with acrylic acid, methacrylic acid, acryl chloride, methacryl chloride, acrylic anhydride, etc. Separately, the poly (oxyalkylene) diacrylate etc. which were manufactured by the well-known method can also be used.

Although the preferable specific example of the monomer corresponding to General formula (2) which can be utilized for manufacture of the fluorine-type polymer which can be used for this invention is given below, this invention is not restrict | limited at all by the following specific examples. Poly (alkyleneoxy) is often a mixture of compounds having different degrees of polymerization X, and the degree of polymerization is expressed by an integer close to the average of the degrees of polymerization in the compounds shown as specific examples.
Moreover, among the exemplary compounds (P-1 to P-141) of the fluorine-based polymer described later, the monomer constituting the portion of the compound corresponding to the repeating unit represented by the general formula (2) is also represented by the general formula ( It is the meaning contained in the preferable specific example of the monomer corresponding to 2).

  The fluoropolymer of the present invention may contain one type of repeating unit derived from the monomer represented by the general formula (1) or (1-1), or may contain two or more types. In addition, as described above, the fluoropolymer of the present invention may have one or two or more kinds of repeating units other than the above repeating units. As an example of this, a monomer capable of a normal radical polymerization reaction is used. A preferred example is a repeating unit derived from. Hereinafter, specific examples of monomers for deriving other repeating units will be given. The fluoropolymer may contain a repeating unit derived from one or two or more monomers selected from the following monomer group.

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

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

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

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

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

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

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

  As the monomer for deriving another repeating unit, a monomer represented by the following general formula (3) is preferably used.

General formula (3)

In the general formula (3), R ⁶ represents a hydrogen atom or a methyl group, Z represents a divalent linking group, and R ⁷ represents a linear or branched chain having 1 to 20 carbon atoms which may have a substituent. Represents a chain or cyclic alkyl group. The divalent linking group represented by Z is preferably an oxygen atom, a sulfur atom, or —N (R ⁵ ) —. Here, R ⁵ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. R ⁵ is more preferably a hydrogen atom or a methyl group.

Examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, which may be linear or branched, Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and the like A polycyclic cycloalkyl group such as a bicycloheptyl group, a bicyclodecyl group, a tricycloundecyl group, a tetracyclododecyl group, an adamantyl group, a norbornyl group, or a tetracyclodecyl group is preferably used.

Examples of the substituent of the alkyl group represented by R ⁷ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarbonyloxy group, a carboxyl group, an alkyl ether group, an aryl ether group, a fluorine atom, a chlorine atom, and a bromine atom. Examples include, but are not limited to, a halogen atom, a nitro group, a cyano group, and an amino group.

  The monomer represented by the general formula (3) is particularly preferably alkyl (meth) acrylate or poly (alkyleneoxy) (meth) acrylate.

  Specific examples of the monomer represented by the general formula (3) are shown below, but the present invention is not limited by the following specific examples.

The fluorine-based polymer used in the present invention is preferably contained in at least two types in the optically anisotropic layer. By containing at least two kinds, it becomes possible to independently improve the unevenness and control the liquid crystal compound, and it becomes easier to have both the surface shape and the viewing angle characteristics.
Here, at least one of the two or more kinds of fluorine-based polymers may be a polymer including a repeating unit derived from the monomer represented by the general formula (1) or (1-1). It is more preferable to include two or more kinds of polymers containing a repeating unit derived from the monomer represented by 1) or (1-1).

  In the fluoropolymer, the amount of the monomer represented by the general formula (1) or (1-1) is preferably 5% by mass or more of the total amount of the polymer contained in the optically anisotropic layer. % Or more is more preferable, and it is further more preferable that it is 30 mass% or more.

  The mass average molecular weight of the fluoropolymer used in the present invention is preferably 1000 to 1,000,000, more preferably 1000 to 500,000, and further preferably 1000 to 100,000. The mass average molecular weight can be measured as a value in terms of polystyrene (PS) using gel permeation chromatography (GPC).

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

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

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

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

  In order to obtain the fluoropolymer in a preferable molecular weight range, a radical polymerization method using a chain transfer agent is particularly effective. As chain transfer agents, mercaptans (for example, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol, p-nonylthiophenol, etc.), polyhalogenated alkyls (for example, carbon tetrachloride, chloroform, etc.) , 1,1,1-trichloroethane, 1,1,1-tribromooctane, etc.) and low-activity monomers (α-methylstyrene, α-methylstyrene dimer, etc.) can be used, preferably carbon These are mercaptans of 4-16. The amount of these chain transfer agents used is remarkably influenced by the activity of the chain transfer agent, the combination of the monomers, the polymerization conditions, etc., and must be precisely controlled, but it is usually preferred for the total number of moles of monomers used. It is 0.01 mol%-50 mol%, More preferably, it is 0.05 mol%-30 mol%, Most preferably, it is 0.08 mol%-25 mol%. These chain transfer agents may be present in the system simultaneously with the target monomer whose degree of polymerization is to be controlled in the polymerization process, and the addition method is not particularly limited. It may be added after being dissolved in the monomer, or may be added separately from the monomer.

  Specific examples of the fluorine-based polymer of the present invention that are preferably used are shown below, but the present invention is not limited to these specific examples. The numerical value in a formula here is a mass percentage which shows the composition ratio of each monomer, respectively, and Mw is the mass mean molecular weight of PS conversion measured by GPC. Numerical values such as a, b, c, and d represent mass ratios. In addition to the following polymer, a repeating unit derived from the exemplified compounds (F-1 to F-89) of the monomer represented by the general formula (1) or (1-1), Exemplary compounds (F-1 to F-89) of monomers represented by the formula (1) or (1-1), monomers corresponding to the general formula (2) (C-1 to -25, A-1 to A) -10) and a polymer containing a repeating unit derived from one or more of the exemplary compounds (A-1 to A-130) of the monomer represented by the general formula (3) are also specific examples of preferred fluorine-based polymers of the present invention. Can be mentioned.

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

  The preferred range of the content of the fluoropolymer in the composition varies depending on the application, but when used for forming the optically anisotropic layer, the composition (a composition excluding the solvent in the case of a coating solution) Among these, 0.005 to 8% by mass is preferable, 0.01 to 5% by mass is more preferable, and 0.05 to 2.5% by mass is even more preferable. By making the addition amount of the fluoropolymer 0.005% by mass or more, the effect of the present invention is more effective, and by making it 8% by mass or less, the coating film is sufficiently dried, What has more preferable performance as an optical compensation sheet (for example, uniformity of retardation, etc.) can be obtained.

The liquid crystalline compound of the present invention is represented by the following general formula (DI).
General formula (DI)

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom.

When Y ¹¹ , Y ¹² and Y ¹³ are methine, the hydrogen atom of methine may be substituted with a substituent. Here, methine refers to an atomic group obtained by removing three hydrogen atoms from methane.
Examples of the substituent that the carbon atom of methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, Halogen atoms and cyano groups can be mentioned as preferred examples. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom and a cyano group are most preferred.
Y ¹¹ , Y ¹² and Y ¹³ are more preferably all methine, and most preferably methine is unsubstituted.

In the general formula (DI), L ¹ , L ² and L ³ each independently represent a single bond or a divalent linking group. When L ¹ , L ² and L ³ are divalent linking groups, each independently represents —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C. It is preferably a divalent linking group selected from the group consisting of ≡C—, a divalent cyclic group, and combinations thereof. R ⁷ is an alkyl group having 1 to ⁷ carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom.

The divalent cyclic group in L ¹ , L ² and L ³ is a divalent linking group having at least one cyclic structure (hereinafter sometimes referred to as a cyclic group). The cyclic group is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring. The ring contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Preferred examples of the aromatic ring include a benzene ring and a naphthalene ring. A preferable example of the aliphatic ring is a cyclohexane ring. Preferred examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring. The cyclic group is more preferably an aromatic ring or a heterocyclic ring. In addition, the divalent cyclic group in the present invention is more preferably a divalent linking group consisting of only a cyclic structure (including a substituent) (hereinafter the same).

Of the divalent cyclic groups represented by L ¹ , L ² and L ³ , the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group.

The divalent cyclic group represented by L ¹ , L ² and L ³ may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms. A halogen-substituted alkyl group, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, and 2 carbon atoms -16 alkoxycarbonyl groups, carbamoyl groups, carbamoyl groups substituted with alkyl groups having 2 to 16 carbon atoms, and acylamino groups having 2 to 16 carbon atoms are included.

L ¹ , L ² and L ³ are each a single bond, * —O—CO—, * —CO—O—, * —CH═CH—, * —C≡C—, * —divalent cyclic group— * -O-CO-divalent cyclic group-, * -CO-O-divalent cyclic group-, * -CH = CH-divalent cyclic group-, * -C≡C-divalent cyclic group Group-, * -divalent cyclic group-O-CO-, * -divalent cyclic group-CO-O-, * -divalent cyclic group-CH = CH- and * -divalent cyclic group- C≡C— is preferred. In particular, a single bond, * —CH═CH—, * —C≡C—, * —divalent cyclic group —O—CO—, * —CH═CH—divalent cyclic group— and * —C≡C -A divalent cyclic group is preferred, and a single bond is most preferred. Here, * represents the position bonded to the 6-membered ring side including Y ¹¹ , Y ¹² and Y ¹³ in the general formula (DI).

H ¹ , H ² and H ³ each independently represent the following general formula (DI-A) or the following general formula (DI-B).

一般式（ＤＩ−Ａ）中、ＹＡ¹およびＹＡ²は、それぞれ独立にメチンのまたは窒素原子を表す。ＹＡ¹およびＹＡ²は、少なくとも一方が窒素原子であることが好ましく、両方が、窒素原子であることがより好ましい。ＸＡは、酸素原子、硫黄原子、メチレンまたはイミノを表し、酸素原子が好ましい。＊は上記一般式（ＤＩ）におけるＬ¹〜Ｌ³側と結合する位置を表し、＊＊は上記一般式（ＤＩ）におけるＲ¹〜Ｒ³側と結合する位置を表す。ここで、イミノは、−ＮＨ−で表されるものをいう。 General formula (DI-A)

In general formula (DI-A), YA ¹ and YA ² each independently represents a methine group or a nitrogen atom. It is preferable that at least one of YA ¹ and YA ² is a nitrogen atom, and it is more preferable that both are nitrogen atoms. XA represents an oxygen atom, a sulfur atom, methylene or imino, and preferably an oxygen atom. * Represents a position bonded to the L ^{1 to} L ³ side in the general formula (DI), and ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (DI). Here, imino means that represented by —NH—.

一般式（ＤＩ−Ｂ）中、ＹＢ¹およびＹＢ²は、それぞれ独立にメチンまたは窒素原子を表す。ＹＢ¹およびＹＢ²は、少なくとも一方が窒素原子であることが好ましく、両方が、窒素原子であることがより好ましい。ＸＢは、酸素原子、硫黄原子、メチレンまたはイミノを表し、酸素原子が好ましい。＊は上記一般式（ＤＩ）におけるＬ¹〜Ｌ³側と結合する位置を表し、＊＊は上記一般式（ＤＩ）におけるＲ¹〜Ｒ³側と結合する位置を表す。 General formula (DI-B)

In the general formula (DI-B), YB ¹ and YB ² each independently represent a methine or a nitrogen atom. It is preferable that at least one of YB ¹ and YB ² is a nitrogen atom, and it is more preferable that both are nitrogen atoms. XB represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom. * Represents a position bonded to the L ^{1 to} L ³ side in the general formula (DI), and ** represents a position bonded to the R ^{1 to} R ³ side in the general formula (DI).

R ¹ , R ² and R ³ each independently represent the following general formula (DI-R).

General formula (DI-R)
*-(-L ²¹ -Q ² ) _n1 -L ²² -L ²³ -Q ¹

In the general formula (DI-R), * represents a position bonded to the H ^{1 to} H ³ side in the general formula (DI).

L ²¹ is a single bond or a divalent linking group. When L ²¹ is a divalent linking group, the group consisting of —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C≡C—, and combinations thereof It is preferably a divalent linking group selected more. R ⁷ is an alkyl group having 1 to ⁷ carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom.

L ²¹ represents a single bond, ***-O-CO-, ***-CO-O-, ***-CH = CH- and ***-C≡C- (where *** Represents a * side in the general formula (DI-R)), and a single bond is more preferable.

Q ² represents a divalent group (cyclic group) having at least one kind of cyclic structure. As such a cyclic group, a cyclic group having a 5-membered ring, a 6-membered ring, or a 7-membered ring is preferable, a cyclic group having a 5-membered ring or a 6-membered ring is more preferable, and a cyclic group having a 6-membered ring is preferable. Further preferred. The cyclic structure contained in the cyclic group may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Preferred examples of the aromatic ring include a benzene ring and a naphthalene ring. A preferable example of the aliphatic ring is a cyclohexane ring. Preferred examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

Of Q ^2, the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. Among these, a 1,4-phenylene group and a 1,4-cyclohexylene group are particularly preferable.

Q ² may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.

  n1 represents the integer of 0-4. n1 is preferably an integer of 1 to 3, and more preferably 1 or 2.

L ²² is **-O-, **-O-CO-, **-CO-O-, **-O-CO-O-, **-S-, **-N (R)-, ** — CH ₂ —, ** — CH═CH— or ** — C≡C— is represented, and ** represents a position bonded to the Q ² side.
L ²² is preferably ** — O—, ** — O—CO—, ** — CO—O—, ** — O—CO—O—, ** — CH ₂ —, ** — CH. ═CH—, ** — C≡C—, more preferably ** — O—, ** — O—CO—, ** — O—CO—O—, ** — CH ₂ —. .

L ²³ is selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH— and —C≡C—, and combinations thereof. Represents a divalent linking group. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ²³ is preferably selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. L ²³ preferably contains 1 to 20 carbon atoms, more preferably 2 to 14 carbon atoms. Furthermore, L ²³ preferably contains 1 to 16 —CH ₂ —, and more preferably ₂ to 12 —CH ₂ —.

Q ¹ represents a polymerizable group or a hydrogen atom. When the liquid crystalline compound used in the present invention is used for an optical compensation sheet or the like that preferably has a phase difference that does not change due to heat, such as an optical compensation sheet, Q ¹ is preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

  Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.

  Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
Among the above formulas (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, more preferably an epoxy group or oxetanyl group, and most preferably an epoxy group.

一般式（ＤＩＩ）中、Ｙ³¹、Ｙ³²およびＹ³³は、それぞれ独立にメチレンまたは窒素原子を表し、一般式（ＤＩ）中の、Ｙ¹¹、Ｙ¹²およびＹ¹³と同義であり、好ましい範囲も同義である。 The liquid crystalline compound used in the present invention is preferably a liquid crystalline compound represented by the following general formula (DII).
Formula (DII)

In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methylene or nitrogen atom and have the same meaning as Y ¹¹ , Y ¹² and Y ^{13 in} the general formula (DI), and a preferred range Is also synonymous.

In the general formula (DII), R ³¹ , R ³² and R ³³ each independently represent the following general formula (DII-R).
General formula (DII-R)

In General Formula (DII-R), A ³¹ and A ³² each independently represent a methylene or nitrogen atom, preferably at least one is a nitrogen atom, and more preferably both are nitrogen atoms. X ³ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

Q ³¹ represents a divalent linking group having a 6-membered cyclic structure (hereinafter sometimes referred to as a 6-membered cyclic group). The 6-membered ring may be a condensed ring. However, it is more preferably a monocycle than a condensed ring. The ring contained in the 6-membered cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocyclic ring. Preferred examples of the aromatic ring include a benzene ring and a naphthalene ring. A preferable example of the aliphatic ring is a cyclohexane ring. Preferred examples of the heterocyclic ring include a pyridine ring and a pyrimidine ring.

Of Q ^31, the 6-membered cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic structure having a naphthalene ring, a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable. The cyclic structure having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic structure having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic structure having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. Among these, a 1,4-phenylene group and a 1,4-cyclohexylene group are particularly preferable.

The cyclic structure of Q ³¹ may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen atom having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 1 carbon atoms 16 alkylthio groups, acyloxy groups having 2 to 16 carbon atoms, alkoxycarbonyl groups having 2 to 16 carbon atoms, carbamoyl groups, alkyl-substituted carbamoyl groups having 2 to 16 carbon atoms, and acylamino groups having 2 to 16 carbon atoms Is included. The substituent of the 6-membered cyclic group is preferably a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group substituted with a halogen atom having 1 to 6 carbon atoms, and further, a halogen atom, An alkyl group having 1 to 4 carbon atoms and an alkyl group substituted with a halogen atom having 1 to 4 carbon atoms are preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.

  n3 represents an integer of 1 to 3, and preferably 1 or 2.

L ³¹ is * -O-, * -O-CO-, * -CO-O-, * -O-CO-O-, * -S-, * -N (R)-, * -CH _2-. , * —CH═CH— or * —C≡C—, * represents a position bonded to the Q ³¹ side, and specifically has the same meaning as L ²² in the general formula (DI-R); The preferred range is also synonymous.

L ³² is selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. It represents a divalent linking group, specifically, the general formula has the same meanings as (DI-R) in L ^23, and the preferred range is also the same.

Q ³² in the general formula (DII-R) represents a polymerizable group or a hydrogen atom.

  Specific examples of the liquid crystal compound represented by the general formula (DI) are shown below, but the present invention is not limited thereto.

  The liquid crystal compound of the present invention desirably exhibits a liquid crystal phase exhibiting good monodomain properties. When the monodomain property is poor, the resulting structure becomes a polydomain, an orientation defect occurs at the boundary between domains, and light is scattered. If good monodomain properties are exhibited, the retardation plate tends to have a high light transmittance.

The liquid crystal phase liquid crystalline compound expressed in the present invention, mention may be made of a columnar phase and a discotic nematic phase (N _D phase). Of these liquid crystal phases, a good monodomain property can and hybrid alignment showed a discotic nematic phase (N _D phase) are most preferred.
In the hybrid alignment, the angle between the physical symmetry axis of the discotic liquid crystalline compound and the surface of the support, that is, the tilt angle is in the direction of the depth of the optically anisotropic layer (that is, perpendicular to the transparent support) and It increases or decreases with increasing distance from the plane of the polarizing film. The angle preferably decreases with increasing distance. In addition, the change in tilt angle can be continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, or intermittent change including increase and decrease. . The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. Even if a region where the angle does not change is included, it may be increased or decreased as a whole. However, it is preferred that the tilt angle changes continuously.

  It can be adjusted by selecting the average direction of the physical symmetry axis of the discotic liquid crystalline compound, generally the material of the discotic liquid crystalline compound or the alignment film, or selecting the rubbing treatment method. Also, the physical symmetry axis direction of the surface side (air side) discotic liquid crystalline compound is generally adjusted by selecting the discotic liquid crystalline compound or the type of additive used together with the discotic liquid crystalline compound. Can do. Here, examples of the additive used together with the discotic liquid crystalline compound include a plasticizer, a surfactant, a polymerizable monomer and a polymer. The degree of change in the orientation direction of the major axis can be adjusted by selecting the liquid crystal compound and the additive as described above.

  The plasticizer, surfactant and polymerizable monomer used in the present invention are compatible with the liquid crystal compound of the present invention and can change the tilt angle of the discotic liquid crystal compound or do not inhibit the alignment. It is preferable. Among the additive components, addition of a polymerizable monomer (eg, a compound having a vinyl group, a vinyloxy group, an acryloyl group and a methacryloyl group) is preferable. In general, the amount of the compound added is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline compound. In addition, when a monomer having 4 or more polymerizable reactive functional groups is mixed and used, adhesion between the alignment film and the optically anisotropic layer can be improved.

  The liquid crystalline compound of the present invention preferably exhibits a liquid crystal phase in the range of 20 ° C to 300 ° C. More preferably, it is 40 degreeC-280 degreeC, Most preferably, it is 60 degreeC-250 degreeC. Here, the expression of the liquid crystal phase at 20 ° C. to 300 ° C. means that the liquid crystal temperature range crosses 20 ° C. (specifically, for example, 10 ° C. to 22 ° C.) or 300 ° C. (specifically, for example, 298). ° C to 310 ° C). The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

  The optical compensation sheet of the present invention is obtained by, for example, applying a composition containing the liquid crystalline compound of the present invention, the fluorine-based polymer of the present invention, and other various compounds to be added as necessary, onto the alignment film, Can be produced by a method including a step of forming an optically anisotropic layer by orienting the molecules. The optically anisotropic layer exhibits optical anisotropy expressed by molecular orientation of the liquid crystalline compound. Hereinafter, among the constituent materials necessary for the optical compensation sheet of the present invention, materials other than the above-described fluoropolymers and liquid crystal compounds will be described in detail.

(Support)
The support of the present invention is preferably transparent, and more preferably glass or a transparent polymer film. The support preferably has a light transmittance of 80% or more. Examples of the polymer constituting the polymer film include cellulose esters (eg, cellulose acetate, cellulose diacetate), norbornene-based polymers, and polymethyl methacrylate. Commercially available polymers (Arton and Zeonex (registered trademark) for norbornene polymers) may be used.
Among these, cellulose esters are preferable, and lower fatty acid esters of cellulose are more preferable. Lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is particularly preferably 2 (cellulose acetate), 3 (cellulose propionate) or 4 (cellulose butyrate). Cellulose acetate is particularly preferred. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate may be used.

In addition, even a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence can be improved in birefringence by modifying the molecule as described in International Publication WO00 / 26705. If controlled, it can be used in the optical compensation sheet of the present invention.
When using the optical compensation sheet of the present invention for a polarizing plate protective film or a retardation film, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5% as the polymer film. The acetylation degree is more preferably 57.0 to 62.0%.

The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation is determined by measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acetate is preferably 250 or more, and more preferably 290 or more. Cellulose acetate preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.0 to 1.65, and most preferably 1.0 to 1.6. preferable.

In cellulose acetate, the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are not evenly substituted, but the substitution degree at the 6-position tends to be small. In the polymer film used in the present invention, it is preferable that the degree of substitution at the 6-position of cellulose is the same or greater than that at the 2- and 3-positions.
The ratio of the substitution degree at the 6-position to the total substitution degree at the 2-position, the 3-position, and the 6-position is preferably 30 to 40%, more preferably 31 to 40%, and more preferably 32 to 40%. Most preferably it is. The substitution degree at the 6-position is preferably 0.88 or more.
The degree of substitution at each position can be measured by NMR.
Cellulose acetate having a high degree of substitution at the 6-position is described in Synthesis Example 1 described in Paragraph Nos. 0043 to 0044, Synthesis Example 2 described in Paragraph Nos. 0048 to 0049, and Paragraph Nos. 0051 to 0052. It can be synthesized with reference to the method of Synthesis Example 3.

(Optically anisotropic layer)
The optically anisotropic layer is preferably designed so as to compensate for the liquid crystalline compound in the liquid crystal cell in the black display of the liquid crystal display device. The alignment state of the liquid crystal compound in the liquid crystal cell in black display varies depending on the mode of the liquid crystal display device. The alignment state of the liquid crystal compound in this liquid crystal cell is described in IDW'00, P411 to 414 of FMC7-2, and the like.
The optically anisotropic layer is formed directly on the support or via an alignment film. The film pressure of the alignment film is preferably 10 μm or less.
The liquid crystalline compound used for the optically anisotropic layer includes a rod-like liquid crystalline compound and a discotic liquid crystalline compound. The rod-like liquid crystal compound and the discotic liquid crystal compound may be a high-molecular liquid crystal or a low-molecular liquid crystal, and further include those in which the low-molecular liquid crystal is cross-linked and no longer exhibits liquid crystallinity.
The optically anisotropic layer can be formed by applying a liquid crystal compound and, if necessary, a coating liquid containing a polymerizable initiator and optional components on the alignment film.
In the present invention, examples of a preferred alignment film include an alignment film described in JP-A-8-338913, which is composed of a crosslinked polymer, more preferably a crosslinked polyvinyl alcohol. The alignment film can be formed using a conventionally known coating method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method). Similarly to the conductive layer, it is preferable to apply and form by a slot die coating method from the viewpoint of uniformity of film thickness, particularly uniformity of film thickness at the end.

As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane, tetrachloroethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
When producing a highly uniform optical compensation sheet as in the present invention, the surface tension is preferably 25 mN / m or less, and more preferably 22 mN / m or less.
The coating liquid can be applied by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).
The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and most preferably 1 to 10 μm.

  Next, a preferred method for applying the optical compensation sheet of the present invention will be described. In the present invention, the alignment film and the optically anisotropic layer are preferably applied by a slot die coating method. Here, the slot die coating method refers to a coating method using a slot coater. FIG. 1 is a schematic view of a slot coater that can be used in the present invention. The coater 10 applies the coating liquid 14 from the slot die 13 as a bead 14a to a web 12 (for example, a transparent film that serves as a support for the optically anisotropic layer) supported by the backup roll 11 and continuously running. As a result, the coating film 14 b is formed on the web 12.

  The slot die 13 has a pocket 15 and a slot 16 formed therein. The pocket 15 has a curved cross section and a straight line. For example, a substantially circular shape as shown in FIG. 1 or a semicircular shape may be used. The pocket 15 is a space extended with the same cross-sectional shape in the width direction of the slot die 13 (in FIG. 1, the direction perpendicular to the paper surface, the same applies hereinafter), and is used to store the coating liquid. Used. The effective length of the extension in the width direction is generally equal to or slightly longer than the coating width (for example, the width of the transparent film). The application liquid 14 is supplied to the pocket 15 from the side surface of the slot die 13 or from the center of the surface opposite to the slot, for example, by a supply pump (not shown) capable of controlling the supply amount. The pocket 15 may be provided with a stopper for preventing the coating liquid 14 from leaking out.

  Similarly to the pocket 15, the slot 16 is a space extended with the same cross-sectional shape in the width direction of the slot die 13, and is a flow path of the coating liquid 14 from the pocket 15 to the web 12. The opening 16a located on the web side is generally adjusted to have a width that is substantially the same as the coating width by using a width regulating plate (not shown) or the like. In general, the angle between the slot 16 and the tangent in the web traveling direction of the backup roll 11 at the tip of the slot is preferably 30 ° to 90 °, but is not limited to this range.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 17a called a land. In this flat portion 17 a, the upstream side of the web 12 in the traveling direction of the web 12 with respect to the slot 16 is hereinafter referred to as an upstream lip land 18 and the downstream side is referred to as a downstream lip land 19.

The length I _LO in the web running direction of the downstream lip land 19 is preferably 30 μm to 500 μm, more preferably 30 μm to 100 μm, and still more preferably 30 μm to 60 μm. Further, the length I _UP of the upstream lip land 18 in the web traveling direction is not particularly limited, but is preferably used in the range of 500 μm to 1 mm.

FIG. 2 is a schematic view (A) of the cross-sectional shape of the slot die 13 and a schematic view (B) of the cross-sectional shape of another slot die 30. In the slot die 30 shown in FIG. 2B, the land length I _LO of the downstream lip land 31 is the same as the length I _UP of the upstream lip land. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 shown in FIG. 2A, the downstream lip land length I _LO is shorter than the upstream lip land length I _UP . In the present invention, a slot die having any shape can be used. However, when coating with a film thickness of 20 μm or less is performed, it is preferable to use a slot die having a shape in which I _LO is shorter than I _UP like the slot die 13. It is preferable because a uniform film thickness can be applied with higher accuracy. Furthermore, the land length I _LO of the downstream lip land 19 is more preferably in the range of 30 μm to 100 μm.

Further, in order to make the film thickness of the coating film uniform with high accuracy, it is preferable that the fluctuation width in the width direction of the slot die 13 of the land length I _LO of the downstream lip land 19 is within 20 μm. If the fluctuation range is within the above range, the beads can be formed more stably, and even if a disturbance or the like occurs, the beads can be prevented from becoming unstable, and the suitability for manufacturing can be maintained.

  The material of the slot die is not particularly limited, but from the viewpoint of improving the strength and surface condition of the tip lip 17 including the opening a of the slot 16, the material of the slot die including at least this portion is made of a carbide material. Is preferred. By using a super hard material, the homogeneity of the surface shape can be improved, and wear of the tip lip due to the coating liquid that is always discharged can be prevented. This is particularly effective when applying a magnetic liquid containing an abrasive as the coating liquid. An example of the super hard material is a material mainly composed of WC. For example, a material prepared by bonding a WC carbide crystal with a bonding metal such as Co can be used. The bonding metal is not limited to Co, and various metals including Ti, Ta, and Nb can also be used. The average particle size of the WC crystal is not particularly limited, but the average particle size is preferably small and is preferably within 5 μm.

Furthermore, in order to maintain the coating thickness of the thin layer uniformly with high accuracy, not only the dimensional accuracy at the tip of the slot die 10 but also the accuracy of the straightness of the backup roll 13 is important. Accordingly, in addition to maintaining the dimensional accuracy in the application width direction of the land length I _LO of the downstream lip land 19, it is preferable that the straightness accuracy of both the tip lip 17 of the slot die 13 and the backup roll 11 is high. The straightness can be determined with sufficient accuracy practically by the following formula (1). However, even a slot die coater that does not satisfy the following formula (1) can be used in the present invention. Here, as shown in FIG. 3, Po is the pressure outside the bead meniscus on the traveling direction side of the web 12, Pp is the internal pressure of the pocket 15, σ is the surface tension of the coating liquid 14, μ is the viscosity of the coating liquid 14a, U Is the coating speed, h is the film thickness, d is the length of the gap between the downstream lip land 19 and the web 12, L is the length of the slot 16 of the slot die 13, and D is the slot gap of the slot die 13. Then, the differential pressure Po-Pp between the internal pressure Pp of the pocket 15 of the slot die 13 and the pressure Po outside the bead meniscus on the web traveling direction side is made constant in the width direction of the slot die 13 and the following equation (1) is used: Find the required straightness. This is because the differential pressure between the pocket 15 of the slot die 13 and the outside of the bead meniscus is constant even if the length d of the gap between the tip of the slot die 13 and the backup roll 11 changes. This is because the flow in the width direction of the die 13 is generated in the pocket 15 and becomes a flow distribution.
Po-Pp = 1.34σ / h ・ (μU / σ) 2/3 + 12μUI _LO (d / 2-h) / d3-12μhUL / D3 (1)

  When coating is performed with a slot die coater under the conditions satisfying the above formula (1), in a coating system used for general industrial production, the coating film thickness distribution is 2% with a straightness in the die block width direction of about 5 μm. Degree (which may differ strictly depending on conditions). Therefore, it can be considered that this limit is the limit when high-precision thin film coating is performed. Thereby, when the slot die 13 is set at the coating position, the straightness of the tip lip and the backup roll is set so that the fluctuation width in the slot die width direction of the gap between the tip lip and the web is within 5 μm. Is preferably maintained.

The optically anisotropic layer contains the fluoroaliphatic polymer of the present invention, but another polymer may be used, and the polymer has the general formula (DI) contained in the optically anisotropic layer. It is preferable that the compound has a certain degree of compatibility with the liquid crystal compound represented by (2) and can change the tilt angle of the liquid crystal compound.
A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose and cellulose acetate butyrate. The amount of the polymer added is preferably in the range of 0.1 to 10% by mass with respect to the liquid crystal compound so as not to inhibit the alignment of the liquid crystal compound of the present invention, and 0.1 to 8% by mass. More preferably, it is in the range of 0.1 to 5% by mass.
The discotic nematic liquid crystal phase-solid phase transition temperature of the liquid crystal compound of the present invention is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.

(Fixing the alignment state of liquid crystalline compounds)
The aligned liquid crystal compound of the present invention can be fixed while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction. For the polymerization reaction, a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator are preferable, and a photopolymerization reaction is more preferable.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Description), acridine and phenazine compounds (JP-A-60-105667, description in US Pat. No. 4,239,850) and oxadiazole compounds (described in US Pat. No. 4,212,970).

The amount of the photopolymerization initiator used is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.5 to 5% by mass, based on the solid content of the coating solution.
The light irradiation for the polymerization of the liquid crystalline compound of the present invention preferably uses ultraviolet rays.
The irradiation energy is preferably in the range of ^{20mJ / cm 2 ~50J / cm 2} , more preferably in the range of ^{20mJ / cm 2 ~5000mJ / cm 2} , a range of 100mJ / cm ² ~800mJ / cm ² More preferably. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.
Furthermore, a protective layer may be provided on the optically anisotropic layer.

(Polarizing film)
The optical compensation sheet of the present invention can exert its functions remarkably by being bonded to a polarizing plate or used as a protective film for protecting the polarizing film of the polarizing plate. In this case, the protective film is very preferably a transparent protective film.
The polarizing film of the present invention is preferably a coating type polarizing film typified by Optiva, or a polarizing film comprising a binder and iodine or a dichroic dye.
Iodine and dichroic dye in the polarizing film exhibit deflection performance by being oriented in the binder. It is preferable that the iodine and the dichroic dye are aligned along the binder molecule, or the dichroic dye is aligned in one direction by self-assembly such as liquid crystal.

A general-purpose polarizer can be prepared, for example, by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath and allowing the iodine or dichroic dye to penetrate into the binder. it can.
In general-purpose polarizing films, iodine or dichroic dye is distributed about 4 μm (about 8 μm on both sides) from the polymer surface, and a thickness of at least 10 μm is necessary to obtain sufficient polarization performance. The penetrability can be controlled by the solution concentration of iodine or dichroic dye, the temperature of the bath, and the immersion time.
As described above, the lower limit of the binder thickness is preferably 10 μm. On the other hand, the upper limit of the thickness is not particularly limited, but the thinner the better, from the viewpoint of the light leakage phenomenon that occurs when the polarizing plate is used in a liquid crystal display device. Currently, it is preferably a general-purpose polarizing plate (about 30 μm) or less, preferably 25 μm or less, and more preferably 20 μm or less. When it is 20 μm or less, the light leakage phenomenon is not observed in a 17-inch liquid crystal display device.

The binder of the polarizing film may be cross-linked. As the crosslinked binder, a polymer that can be crosslinked per se can be used. A polarizing film can be formed by reacting a polymer having a functional group or a binder obtained by introducing a functional group into a polymer between the binders by light, heat, or pH change.
Moreover, you may introduce | transduce a crosslinked structure into a polymer with a crosslinking agent. It can be formed by cross-linking between binders by introducing a bonding group derived from the cross-linking agent between binders using a cross-linking agent which is a compound having high reaction activity.
Crosslinking is generally carried out by applying a coating solution containing a polymer or a mixture of a polymer and a crosslinking agent on a transparent support and then heating. Since it is only necessary to ensure durability at the stage of the final product, the crosslinking treatment may be performed at any stage until the final polarizing plate is obtained.

  As the binder of the polarizing film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used. Examples of polymers include polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, polystyrene, gelatin, polyvinyl alcohol, modified polyvinyl alcohol, poly (N-methylolacrylamide), polyvinyltoluene, chlorosulfonated polyethylene, nitrocellulose, chlorinated Polyolefin (eg, polyvinyl chloride), polyester, polyimide, polyvinyl acetate, polyethylene, carboxymethyl cellulose, polypropylene, polycarbonate and copolymers thereof (eg, acrylic acid / methacrylic acid polymer, styrene / maleimide polymer, styrene / vinyl) Toluene polymer, vinyl acetate / vinyl chloride polymer, ethylene / vinyl acetate polymer). Water-soluble polymers (eg, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol and modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred, and polyvinyl alcohol and modified polyvinyl alcohol are most preferred. .

The saponification degree of polyvinyl alcohol and modified polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%, and most preferably 95 to 100%. As for the polymerization degree of polyvinyl alcohol, 100-5000 are preferable.
Modified polyvinyl alcohol is obtained by introducing a modifying group into polyvinyl alcohol by copolymerization modification, chain transfer modification or block polymerization modification. In the copolymerization modification, —COONa, —Si (OH) ₃ , N (CH ₃ ) ₃ .Cl, C ₉ H ₁₉ COO—, —SO ₃ Na, —C ₁₂ H ₂₅ may be introduced as modifying groups. it can. In chain transfer modification, —COONa, —SH, or —SC ₁₂ H ₂₅ can be introduced as a modifying group. The degree of polymerization of the modified polyvinyl alcohol is preferably 100 to 3000. The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127.
Unmodified polyvinyl alcohol and alkylthio-modified polyvinyl alcohol having a saponification degree of 85 to 95% are particularly preferable.
Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

When a large amount of the crosslinking agent for the binder is added, the heat and humidity resistance of the polarizing film can be improved. However, when 50 mass% or more of a crosslinking agent is added to the binder, the orientation of iodine or the dichroic dye is lowered. 0.1-20 mass% is preferable with respect to a binder, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable.
The binder contains some crosslinking agent that has not reacted even after the crosslinking reaction has been completed. However, the amount of the remaining crosslinking agent is preferably 1.0% by mass or less in the binder, and more preferably 0.5% by mass or less. When the crosslinking agent is contained in the binder layer in an amount exceeding 1.0% by mass, there may be a problem in durability. That is, when a polarizing film having a large amount of residual crosslinking agent is incorporated in a liquid crystal display device and used for a long time or left in a high-temperature and high-humidity atmosphere for a long time, the degree of polarization may decrease.
The crosslinking agent is described in US Reissue Patent 23297. Boron compounds (eg, boric acid, borax) can also be used as a crosslinking agent.

As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (eg, sulfo group, amino group, hydroxyl group).
Examples of dichroic dyes include C.I. I. Direct Yellow 12, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Red 39, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Direct Violet 48, C.I. I. Direct Blue 67, C.I. I. Direct Blue 90, C.I. I. Direct Green 59, C.I. I. Acid Red 37 is included. As for the dichroic dyes, those described in JP-A-1-161202, 1-172906, 1-172907, 1-183602, 1-248105, 1-265205, 7-261024 are used. There are descriptions in each publication. The dichroic dye is used as a free acid or an alkali metal salt, ammonium salt or amine salt. By blending two or more kinds of dichroic dyes, polarizing films having various hues can be produced. A polarizing film using a compound (pigment) that exhibits a black color when the polarization axes are orthogonal to each other, or a polarizing film or a polarizing plate in which various dichroic molecules are blended so as to exhibit a black color, have both a single-plate transmittance and a polarizability. It is excellent and preferable.

  In order to increase the contrast ratio of the liquid crystal display device, the transmittance of the polarizing plate is preferably higher and the degree of polarization is preferably higher. The transmittance of the polarizing plate is preferably in the range of 30 to 50%, more preferably in the range of 35 to 50%, and in the range of 40 to 50% in the light having a wavelength of 550 nm (of the polarizing plate). Most preferably, the maximum value of the single plate transmittance is 50%. The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.

  It is also possible to dispose the polarizing film and the optically anisotropic layer, or the polarizing film and the alignment film via an adhesive. As the adhesive, a polyvinyl alcohol resin (including a modified polyvinyl alcohol with an acetoacetyl group, a sulfonic acid group, a carboxyl group, or an oxyalkylene group) or an aqueous boron compound solution can be used. Of these, polyvinyl alcohol resins are preferred. The thickness of the adhesive layer is preferably in the range of 0.01 to 10 μm after drying, and particularly preferably in the range of 0.05 to 5 μm.

(Manufacture of polarizing plates)
From the viewpoint of yield, the polarizing film is stretched at an angle of 10 to 80 degrees with respect to the longitudinal direction (MD direction) of the polarizing film (stretching method) or rubbed (rubbing method). It is preferable to dye with a dichroic dye. The tilt angle is preferably stretched so as to match the angle formed between the transmission axis of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the vertical or horizontal direction of the liquid crystal cell.
A normal inclination angle is 45 degrees. Recently, however, devices that are not necessarily 45 degrees have been developed in transmissive, reflective, and transflective LCDs, and it is preferable that the stretching direction can be arbitrarily adjusted in accordance with the design of the LCD.

In the stretching method, the stretching ratio is preferably 2.5 to 30.0 times, and more preferably 3.0 to 10.0 times. Stretching can be performed by dry stretching in air. Moreover, you may implement wet extending | stretching in the state immersed in water. The stretch ratio of dry stretching is preferably 2.5 to 5.0 times, and the stretch ratio of wet stretching is preferably 3.0 to 10.0 times. The stretching step may be performed in several steps including oblique stretching. By dividing into several times, it is possible to stretch more uniformly even at high magnification. Before the oblique stretching, a slight stretching (a degree to prevent shrinkage in the width direction) may be performed horizontally or vertically.
Stretching can be performed by performing tenter stretching in biaxial stretching in different steps. The biaxial stretching is the same as the stretching method performed in normal film formation. In biaxial stretching, stretching is performed at different speeds on the left and right, so that the thickness of the binder film before stretching needs to be different on the left and right. In casting film formation, the flow rate of the binder solution can be differentiated between the left and right sides by tapering the die.
As described above, a binder film that is obliquely stretched by 10 to 80 degrees with respect to the MD direction of the polarizing film is produced.

In the rubbing method, a rubbing treatment method widely adopted as a liquid crystal alignment treatment process of LCD can be applied. That is, the orientation is obtained by rubbing the surface of the film in a certain direction using paper, gauze, felt, rubber, nylon, or polyester fiber. In general, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are planted on average. It is preferable to carry out using a rubbing roll in which the roundness, cylindricity, and deflection (eccentricity) of the roll itself are 30 μm or less. The film wrap angle on the rubbing roll is preferably 0.1 to 90 degrees. However, as described in JP-A-8-160430, a stable rubbing treatment can be obtained by winding 360 degrees or more.
When rubbing a long film, the film is preferably transported at a speed of 1 to 100 m / min in a constant tension state by a transport device. The rubbing roll is preferably rotatable in the horizontal direction with respect to the film traveling direction for setting an arbitrary rubbing angle. It is preferable to select an appropriate rubbing angle in the range of 0 to 60 degrees. When used in a liquid crystal display device, 40 to 50 degrees is preferable. 45 degrees is particularly preferable.
It is preferable to dispose a polymer film (arrangement of optically anisotropic layer / polarizing film / polymer film) on the surface of the polarizing film opposite to the optically anisotropic layer.

  Hereinafter, a preferred form of the optically anisotropic layer in each liquid crystal mode in the liquid crystal display device will be described.

(TN mode liquid crystal display)
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.
The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which a rod-like liquid crystalline molecule rises at the center of the cell and the rod-like liquid crystalline compound lies in the vicinity of the cell substrate.

The rod-like liquid crystalline compound in the center of the cell is compensated with a discotic liquid crystalline compound of the homeotropic orientation (horizontal orientation in which the disk surface is lying) or a (transparent) support, and the rod-like liquid crystalline property in the vicinity of the cell substrate The compound can be compensated with a discotic liquid crystalline compound having a hybrid alignment (an alignment in which the inclination of the major axis changes with the distance from the polarizing film).
In addition, the rod-like liquid crystalline compound at the center of the cell is compensated with a rod-like liquid crystalline compound having a homogeneous orientation (horizontal orientation in which the major axis lies) or a (transparent) support, and the rod-like liquid crystalline property in the vicinity of the cell substrate is compensated. The compound can be compensated with a discotic liquid crystalline compound having a hybrid alignment.

The homeotropic alignment liquid crystal compound is aligned in a state where the angle between the average alignment direction of the major axis of the liquid crystal compound and the plane of the polarizing film is 85 to 95 degrees.
The liquid crystal compound of homogeneous alignment is aligned with the angle between the average alignment direction of the major axis of the liquid crystal compound and the plane of the polarizing film being less than 5 degrees.
In the hybrid alignment liquid crystalline compound, the angle between the long axis average alignment direction of the liquid crystalline compound and the plane of the polarizing film is preferably 15 degrees or more, and more preferably 15 degrees to 85 degrees.

(Transparent) Optically anisotropic layer in which the support or discotic liquid crystalline compound is homeotropically oriented, optically anisotropic layer in which rod-like liquid crystalline compound is homogeneously oriented, or homeotropically oriented discotic An optically anisotropic layer made of a mixture of a liquid crystal compound and a homogeneously oriented rod-like liquid crystal compound has a retardation value (Rth) in the thickness direction of 40 nm to 200 nm, and an in-plane retardation value (Re). It is preferable that it is 0-70 nm.
In the present specification, Re and Rth respectively represent in-plane retardation and retardation in the thickness direction. Re is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments) by making light incident in the normal direction of the film. Rth is the retardation value measured by making light incident from the direction inclined by + 40 ° with respect to the film normal direction, with the above-mentioned Re, in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis) And retardation measured in three directions, the retardation value measured by making light incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) KOBRA 21ADH is calculated based on the value. Here, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical compensation sheets can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of the main optical compensation sheets are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49) Polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting these assumed values of average refractive index and film thickness.
Regarding the discotic liquid crystal compound layer having homeotropic alignment (horizontal alignment) and the rod-like liquid crystal compound layer having homogeneous alignment (horizontal alignment), Japanese Patent Laid-Open Nos. 12-304931 and 12-304932 describe them. Are listed. The discotic liquid crystal compound layer having a hybrid orientation is described in JP-A-8-50206.

(OCB mode liquid crystal display)
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which a rod-like liquid crystal compound is aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. Liquid crystal display devices using a bend alignment mode liquid crystal cell are disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal compounds are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is called an OCB (Optically Compensatory Bend) liquid crystal mode.
Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystal compound rises at the center of the cell and the rod-like liquid crystal compound lies in the vicinity of the cell substrate. .

  Since the TN mode and the liquid crystal orientation are the same in black display, the preferred mode is the same as that for the TN mode. However, since the OCB mode has a larger range in which the liquid crystal compound has risen at the center of the cell than the TN mode, an optically anisotropic layer in which the discotic liquid crystal compound is homeotropically aligned or a rod-like liquid crystal It is necessary to slightly adjust the retardation value of the optically anisotropic layer in which the functional compound is homogeneously oriented. Specifically, the optically anisotropic layer in which the discotic liquid crystalline compound on the (transparent) support is homeotropically oriented, or the optically anisotropic layer in which the rod-like liquid crystalline compound is homogeneously oriented has a thickness of The longitudinal retardation value (Rth) is preferably 150 nm to 500 nm, and the in-plane retardation value (Re) is preferably 20 to 70 nm.

(VA mode liquid crystal display device)
In the VA mode liquid crystal cell, the rod-like liquid crystalline compound is aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which a rod-like liquid crystal compound is aligned substantially vertically when no voltage is applied, and is substantially horizontally aligned when a voltage is applied (Japanese Patent Laid-Open No. 2). 176625 (in Japanese Patent Publication No. 176625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which a rod-like liquid crystalline compound is substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary Collection 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  In the black display of the VA mode liquid crystal display device, most of the rod-like liquid crystalline compounds in the liquid crystal cell are in a standing state, so that the optically anisotropic layer in which the discotic liquid crystalline compounds are homeotropically aligned, Alternatively, the liquid crystal compound is compensated for by the optically anisotropic layer in which the rod-like liquid crystal compound is homogeneously oriented, and the rod-like liquid crystal compound is homogeneously oriented, and the average orientation direction of the major axis of the rod-like liquid crystal compound and the polarizing film It is preferable to compensate the viewing angle dependency of the polarizing plate with an optically anisotropic layer having an angle with respect to the transmission axis direction of less than 5 degrees.

  (Transparent) The optically anisotropic layer in which the support or the discotic liquid crystalline compound is homeotropically oriented, or the optically anisotropic layer in which the rod-like liquid crystalline compound is homogeneously oriented has a retardation value in the thickness direction. (Rth) is preferably 150 nm to 500 nm, and the in-plane retardation value (Re) is preferably 20 to 70 nm.

(Other liquid crystal display devices)
The ECB mode and STN mode liquid crystal display devices can be optically compensated in the same way as described above.

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

(Synthesis of fluoroaliphatic group-containing polymer (P-33))

In a reactor equipped with a stirrer and a reflux condenser, 39.13 g of 1H, 1H, 7H-dodecafluoroheptyl acrylate, 0.80 g of acrylic acid, 1.1 g of dimethyl 2,2′-azobisisobutyrate, 2-butanone 30 g was added and heated to 78 ° C. for 6 hours under a nitrogen atmosphere to complete the reaction. The mass average molecular weight was 1.0 × 10 ⁴ .

  Fluorine polymers (P-34), (P-136), and (P-138) were synthesized by the same method as the synthesis method of the fluoroaliphatic group-containing polymer (P-33).

[Example 1]
(Production of polymer substrate)
The following composition was put into a mixing tank and stirred while heating to 30 ° C. to dissolve each component to prepare a cellulose acetate solution.

  The obtained inner layer dope and outer layer dope were cast on a drum cooled to 0 ° C. using a three-layer co-casting die. The film having a residual solvent amount of 70% by mass was peeled off from the drum, both ends were fixed with a pin tenter, and the film was dried at 80 ° C. while transporting at a draw ratio of 110% in the transport direction, resulting in a residual solvent amount of 10%. By the way, it was dried at 110 ° C. Thereafter, it was dried at 140 ° C. for 30 minutes to produce a cellulose acetate film (outer layer: 3 μm, inner layer: 74 μm, outer layer: 3 μm) having a residual solvent of 0.3 mass%. The optical properties of the produced cellulose acetate film (CF-02) were measured.

The obtained polymer substrate (PK-1) had a width of 1340 mm and a thickness of 80 μm. It was 6 nm when the retardation value (Re) in wavelength 500nm was measured using the ellipsometer (M-150, JASCO Corporation make). Further, the retardation value (Rth) in the thickness direction at a wavelength of 500 nm was measured and found to be 83 nm.
The produced polymer substrate (PK-1) was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried. The surface energy of this PK-1 was determined by the contact angle method and found to be 63 mN / m.

  In the production of the optical compensation sheet, the slot die shown in FIG. 2A was incorporated into the slot coater shown in FIG. As shown in FIG. 1, the web 12 is fed by a feeding machine and proceeds to a coating process through a rubbing treatment roll while being supported by the roll. Then, it passes through a drying zone, a heating zone, and an ultraviolet lamp, and is wound up by a winder. In addition, the decompression chamber was installed in the position which does not contact on the opposite side to the advancing direction side of the web 12 so that sufficient decompression adjustment with respect to the bead 14a can be performed.

The alignment film and the optically anisotropic layer were produced by a slot die coating method. That is, the upstream lip land length I _UP of the slot die 13 is 1 mm, the downstream lip land length I _LO is 50 μm, and the coating solution 14 is applied on the web 12 at 5 ml / m ² so that the wet film thickness is 5 μm. did. The coating speed was 60 m / min. For the web 12, the above-described cellulose triacetate substrate having a thickness of 80 μm was used, and the length of the gap between the downstream lip land 19 and the cellulose triacetate substrate as the web 12 was set to 40 μm. Before coating the coating liquid 14 (optically anisotropic layer composition), the alignment film is coated on the coated surface of the web 12 with the following composition, heated at 60 ° C. for 60 seconds, and further heated at 90 ° C. The resin layer for alignment films was formed by drying for 150 seconds with wind. The web 12 on which the alignment layer resin layer is formed in advance is fed, and the surface of the alignment layer resin layer is rubbed to form an alignment layer, which is then conveyed to the coating process and coated (optically anisotropic layer composition). Carried out. In the rubbing treatment, the alignment film was rubbed in a direction parallel to the slow axis (measured at a wavelength of 632.8 nm) of the polymer substrate (PK-1). The rotational peripheral speed of the rubbing roller in the rubbing treatment was 5.0 m / sec, and the pressing pressure against the alignment layer resin layer was set to 9.8 × 10 ⁻³ Pa.

(Orientation film coating solution composition)
The following modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde (crosslinking agent) 0.5 parts by weight

  As the coating solution 14, the composition of the optically anisotropic layer shown below was used. The coating speed was 60 m / min. The web 12 coated with the coating liquid 14 is passed through a drying zone set at 100 ° C. and a heating zone set at 130 ° C., and ultraviolet rays are irradiated on the surface of the liquid crystal layer by a 120 W / cm UV lamp in an atmosphere at 60 ° C. Irradiated to produce an optical compensation sheet (KH-1). The applicability was judged by visual observation of the bead state, and the application was impossible when the bead 14a was broken. As a result, in Example 1, application was possible, and the degree of vacuum at this time was 1000 Pa.

(Optically anisotropic layer composition)
The following composition was dissolved in 102 kg of methyl ethyl ketone to prepare a coating solution.
Liquid crystalline compound (D38) 41.01 parts by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4.06 parts by mass cellulose acetate butyrate (CAB551-0.2, Eastman) 0.34 parts by mass cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co., Ltd.) 0.11 parts by mass of fluoroaliphatic group-containing polymer exemplified compound (P-33) 0.018 parts by mass of fluoroaliphatic Group-containing polymer exemplified compound (P-136) 0.23 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 1.35 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0. 45 parts by mass

  The Re retardation value of the optically anisotropic layer measured at a wavelength of 546 nm was 50 nm. Moreover, when the polarizing plate was arranged in a crossed Nicol arrangement and the unevenness of the obtained optical compensation sheet was observed, no unevenness was detected even when viewed from the front and the direction inclined by 60 degrees from the normal line.

(Evaluation of tilt angle of liquid crystal compounds)
In an optically anisotropic layer in which a discotic liquid crystalline compound or a rod-like liquid crystalline compound is aligned, a tilt angle on one surface of the optically anisotropic layer (a physical target axis in a discotic liquid crystalline compound or a rod-like liquid crystalline compound) It is difficult to directly and accurately measure θ1 and the tilt angle θ2 of the other surface. Therefore, in this specification, θ1 and θ2 are calculated by the following method. Although this method does not accurately represent the actual orientation state of the present invention, it is effective as a means for expressing the relative relationship of some optical characteristics of the optical compensation sheet.
In this method, in order to facilitate calculation, the following two points are assumed and the tilt angle at the two interfaces of the optically anisotropic layer is used.
1. It is assumed that the optically anisotropic layer is a multilayer body composed of layers containing a discotic liquid crystalline compound or a rod-like liquid crystalline compound. Further, it is assumed that the minimum unit layer (the tilt angle of the discotic liquid crystal compound or the rod-like liquid crystal compound is uniform in the layer) constituting it is optically uniaxial.
2. It is assumed that the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer.
Specifically, it was calculated by the following calculation method.
(1) In a plane in which the tilt angle of each layer changes monotonically with a linear function along the thickness direction of the optically anisotropic layer, the incident angle of the measurement light to the optically anisotropic layer is changed, and three or more The retardation value is measured at the measurement angle. In order to simplify the measurement and calculation, the normal direction with respect to the optically anisotropic layer was set to 0 °, and the retardation value was measured at three measurement angles of −40 °, 0 °, and + 40 °. This measurement was performed with KOBRA-21ADH (manufactured by Oji Scientific Instruments). KOBRA-WR (manufactured by Oji Scientific Instruments), transmission type ellipsometer AEP-100 (manufactured by Shimadzu Corporation), M150 and M520 (manufactured by JASCO Corporation), ABR10A (Uniopt Co., Ltd.) The same result can be obtained even if it is carried out in the above.
(2) In the above model, the refractive index of ordinary light in each layer is no, the refractive index of extraordinary light is ne (ne is the same value in all layers, and no is the same), and the thickness of the entire multilayer body is d. And Further, based on the assumption that the tilt direction of each layer and the uniaxial optical axis direction of the layer coincide with each other, the calculation of the angular dependence of the retardation value of the optically anisotropic layer agrees with the measured value. Fitting is performed using the tilt angle θ1 on one surface of the isotropic layer and the tilt angle θ2 on the other surface as variables, and θ1 and θ2 are calculated. The results are shown in Table 1.
Here, known values such as literature values and catalog values can be used for no and ne. If the value is unknown, it can also be measured using an Abbe refractometer. The thickness of the optically anisotropic layer can be measured by an optical interference film thickness meter, a cross-sectional photograph of a scanning electron microscope, or the like.

(Preparation of polarizing plate)
Using a polyvinyl alcohol-based adhesive, KH-1 (optical compensation sheet) was attached to one surface of the polarizer (HF-1). Further, a saponification treatment was performed on a 80 μm-thick triacetyl cellulose film (TD-80U: manufactured by Fuji Photo Film Co., Ltd.), and the opposite surface of the polarizer (HF-1) using a polyvinyl alcohol adhesive. Pasted on.
The transmission axis of the polarizer (HF-1) and the slow axis of the polymer film (PK-1) which is a support for the optical compensation sheet were arranged in parallel. The transmission axis of the polarizer (HF-1) and the slow axis of the triacetyl cellulose film were arranged so as to be orthogonal to each other. In this way, a polarizing plate (HB-1) was produced.

(Evaluation with TN liquid crystal cell)
A pair of polarizing plates provided in a liquid crystal display device (AQUAS LC20C1S, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and the produced polarizing plate (HB-1) is replaced with an optical compensation sheet. A single sheet was affixed to the observer side and the backlight side via an adhesive so that (KH-1) was on the liquid crystal cell side. The transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side were arranged to be in the O mode.
About the produced liquid crystal display device, the viewing angle was measured from the black display (L1) to the white display (L8) using the measuring machine (BM-5A, TOPCON company make). A region having a contrast ratio (white transmittance / black transmittance) of 10 or more and no gradation inversion on the black side (inversion at L1 and L2) was obtained as a viewing angle. The measurement results are shown in Table 2.

(Evaluation of unevenness on LCD panel and evaluation of upper viewing angle color)
The display panel of the liquid crystal display device was adjusted to a halftone on the entire surface, and unevenness was evaluated. Moreover, the change of the color seen from the front direction at the time of black display and the color seen from the upper 60 ° direction was evaluated. (If Δu′v ′ ≦ 0.045 or less, ○, Δu′v ′> 0.045 is x). The following Examples 2 to 4 and Comparative Examples 1 to 4 were similarly evaluated. Δu′v ′ was indexed by the color difference according to the CIE 1976 UCS chromaticity diagram.

[Examples 2-3, Comparative Examples 1-3]
As shown in Table 1, an optical compensation sheet was prepared in the same manner as in Example 1 except that the type and addition amount of the fluoroaliphatic group-containing polymer and the type of liquid crystal compound were changed. Corner, unevenness, and tint were evaluated. The results are shown in Table 1.

Discotic liquid crystal compound (DLC-1)

  As can be seen from the results shown in Table 1, a uniform surface shape can be realized by using the fluoroaliphatic group-containing polymer and the liquid crystalline compound of the present invention. Further, by using two types in combination, a liquid crystal display device having good viewing angle and color display characteristics can be provided.

[Example 4]
The same procedure as in Example 1 was conducted, except that the addition amount of the retardation increasing agent used in Example 1 was changed to prepare polymer base materials having retardations in the thickness direction of 76, 83, 100, and 110 nm. An optical compensation sheet and a polarizing plate with an optical compensation sheet were prepared. Even when the retardation in the thickness direction of the polymer substrate was changed to 76, 83, 100, and 110 nm, it was confirmed that the surface was uniform and display characteristics of viewing angle and color were good.

[Example 5]
The retardation increasing agent used in Example 1 was replaced with the following retardation increasing agent, and the addition amount of the inner layer was 1.2 parts by mass, and a polymer base material having a thickness direction retardation of 90 nm was prepared. Were prepared in the same manner as in Example 1 to produce an optical compensation sheet, and further a polarizing plate with an optical compensation sheet. It was confirmed that the display characteristics of viewing angle and color were good with a flat surface with no unevenness.

[Example 6]
The same procedure as in Example 1 was performed except that the addition amount of the retardation increasing agent used in Example 5 was changed to prepare a polymer base material having retardation in the thickness direction of 76, 83, 100, and 110 nm. An optical compensation sheet and a polarizing plate with an optical compensation sheet were prepared. Even when the retardation in the thickness direction of the polymer substrate was changed to 76, 83, 100, and 110 nm, it was confirmed that the surface was uniform and display characteristics of viewing angle and color were good.

It is the schematic of the slot coater which can be utilized for this invention. FIG. 2 is a schematic view (A) of the cross-sectional shape of the slot die 13 in FIG.

Explanation of symbols

10 Coater 11 Backup Roll 12 Web 13 Slot Die 14 Coating Solution 15 Pocket 16 Slot 17 Tip Lip 18 Upstream Lip Land 19 Downstream Lip Land 30 Slot Die 31 Downstream Lip Land 32 Symbol 33 Slot

Claims (8)

At least one fluoroaliphatic group-containing polymer containing a repeating unit derived from a monomer represented by the following general formula (1) and general formula (1-1), and a liquid crystal property represented by the following general formula (DI) An optical compensation sheet having an optically anisotropic layer containing a compound.
General formula (1)

(In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Z represents a hydrogen atom or a fluorine atom, m represents an integer of 1 to 6, and n represents an integer of 2 to 4.)
General formula (1-1)

(In General Formula (1-1), A is selected from a divalent (q = 1) or trivalent (q = 2) linking group selected from the following linking group group A, or a linking group group A described below. represents a linking group of bivalent formed by combining two or more (q = 1) or trivalent (q = 2), also linking groups to each other may be bonded via an oxygen atom, Z ¹ is A hydrogen atom or a fluorine atom is represented, p is an integer of 3-8, q represents 1 or 2.)
(Linking group A)
_{-CH 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, - C 6 H 4 - and _{-C 6 H 3 <(- C} 6 H 4 - and -C ₆ H ₃ <benzene The substitution position on the ring may be any position.)
General formula (DI)

(In General Formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom, and L ¹ , L ² and L ³ each independently represents a single bond or a divalent linking group. H ¹ , H ² and H ³ each independently represent the following general formula (DI-A) or the following general formula (DI-B), and R ¹ , R ² and R ³ each independently represent the following general formula Represents formula (DI-R).)
General formula (DI-A)

(In the general formula (DI-A), YA ¹ and YA ² each independently represents a methine or nitrogen atom, XA represents an oxygen atom, a sulfur atom, methylene or imino, and * represents the above general formula (DI). Represents the position of bonding to the L ^{1 to} L ³ side in **, and ** represents the position of bonding to the R ^{1 to} R ³ side in the general formula (DI).)
General formula (DI-B)

(In the general formula (DI-B), YB ¹ and YB ² each independently represent a methine or nitrogen atom, XB represents an oxygen atom, a sulfur atom, methylene or imino. * Represents the above general formula (DI) Represents the position of bonding to the L ^{1 to} L ³ side in **, and ** represents the position of bonding to the R ^{1 to} R ³ side in the general formula (DI).)
General formula (DI-R)
*-(-L ²¹ -Q ² ) _n1 -L ²² -L ²³ -Q ¹
(In the general formula (DI-R), * represents a position bonded to the H ^{1 to} H ³ side in the general formula (DI), L ²¹ represents a single bond or a divalent linking group, and Q ² represents at least 1; N1 represents an integer of 0 to 4, L ²² represents **-O-, **-O-CO-, **-CO-O-, * * -O-CO-O -, ** - S -, * - N (R) -, ** - CH 2 -, ** - CH = CH- or ** - C≡C- represent, ** Represents a position bonded to the Q ² side, and L ²³ represents —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH— and —C≡C. -Represents a divalent linking group selected from the group consisting of these, and Q ¹ represents a polymerizable group or a hydrogen atom, and when n1 is 2 or more, a plurality of -L ²¹ -Q ² are each , Same or different Even if it is.) The optical compensation sheet according to claim 1, wherein the liquid crystalline compound represented by the general formula (DI) is represented by the following general formula (DII).
Formula (DII)

(In the general formula (DII), Y ³¹ , Y ³² and Y ³³ each independently represent a methine or nitrogen atom, and R ³¹ , R ³² and R ³³ each independently represents the following general formula (DII-R) To express.)
General formula (DII-R)

(In the general formula (DII-R), A ³¹ and A ³² each independently represent a methine or nitrogen atom, X ³ represents an oxygen atom, a sulfur atom, methylene or imino, and Q ³¹ represents a 6-membered cyclic group. represents a divalent linking group having a structure, n3 represents an integer of 1 to 3, L ³¹ is * -O -, * - O- CO -, * - CO-O -, * - O-CO- O-, * -S-, * -N (R)-, * -CH _2- , * -CH = CH- or * -C≡C-, * represents a position bonded to the Q ³¹ side, L ³² is selected from the group consisting of —O—, —S—, —C (═O) —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Represents a divalent linking group, and Q ³² represents a polymerizable group or a hydrogen atom. When n3 is 2 or more, each Q ³¹ may be the same or different. The fluoroaliphatic group-containing polymer containing a repeating unit derived from the monomer represented by the general formula (1) is included, and Z in the general formula (1) is a hydrogen atom. Optical compensation sheet. The optical compensation sheet according to any one of claims 1 to 3, wherein the fluoroaliphatic group-containing polymer is a polymer further comprising a repeating unit represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ²¹ , R ²² and R ²³ each represent a hydrogen atom or a substituent, L is a single bond, —O—, —CO—, —NR ²⁴ — (R ²⁴ is hydrogen) An atom, an alkyl group, an aryl group or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ²⁵ ) — (R ²⁵ represents an alkyl group, an aryl group or an aralkyl group), Represents a divalent linking group consisting of one or more groups selected from the group consisting of an alkylene group and an arylene group, and Q represents an unsubstituted carboxyl group or a salt thereof, an unsubstituted sulfo group or a salt thereof, or {-OP (= O) (OH) ₂ } or a salt thereof, or a group containing a poly (alkyleneoxy) group. The optically anisotropic layer contains at least two fluoroaliphatic group-containing polymers, and at least one of the fluoroaliphatic group-containing polymers is represented by the general formula (1) or (1-1). The optical compensation sheet according to any one of claims 1 to 4, which is a fluoroaliphatic group-containing polymer containing a repeating unit derived from a monomer. The optically anisotropic layer is provided on an alignment film, and the alignment film and / or the optically anisotropic layer is applied by a slot die coating method. Optical compensation sheet. An elliptically polarizing plate having at least a polarizing film and a protective film provided on one surface of the polarizing film, wherein the protective film is the optical compensation sheet according to claim 1. A liquid crystal display device comprising the elliptically polarizing plate according to claim 7.

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