JP2005179636A - Composition, optical compensation sheet using the composition, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical compensation sheet having a good optical compensation function. <P>SOLUTION: The optical compensation sheet having an optical anisotropic layer formed of a composition containing a liquid crystal compound, at least one type of polymer with a side chain that contains 1 or more types of hydrophilic group selected from the group consisting of fluoroaliphatic group, carboxyl group (-COOH), sulfo group (-SO<SB>3</SB>H), phosphonoxy [-OP(=O)(OH)<SB>2</SB>], and salts thereof. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an optical compensation sheet having an optical anisotropy layer exhibiting optical anisotropy expressed by alignment of liquid crystal molecules and having an excellent optical compensation function. The present invention also relates to a polarizing plate and a liquid crystal display device using the optical compensation sheet. Furthermore, the present invention relates to a composition useful for producing an optical compensation sheet or the like.

  An optical compensation sheet having an optically anisotropic layer in which liquid crystal molecules are aligned (hybrid alignment) so that the tilt angle changes with the distance to the transparent support is TN (Twisted Nematic) mode or OCB (Optically Compensatory). An optical compensation sheet having an optically anisotropic layer made of a discotic liquid crystalline compound that is useful for enlarging the viewing angle of a Bend mode liquid crystal display device and aligned at a tilt angle of 5 to 50 degrees has been proposed ( For example, see Patent Literature 1 and Patent Literature 2). For this optically anisotropic layer, a composition containing a discotic liquid crystal compound is usually applied on the alignment film, heated to a temperature higher than the alignment temperature to align the discotic liquid crystalline molecules, and the alignment state is fixed. It is formed by doing.

  On the other hand, in order to obtain a desired optical compensation capability, it is necessary to increase the tilt angle on the air interface side. As a method for obtaining an angle exceeding 50 ° which is a tilt angle obtained at a normal air interface, a method of adding a partially esterified cellulose has been proposed (for example, see Patent Document 3). In addition, there is a method in which a compound having a fluorine-substituted alkyl group and a hydrophilic group (a sulfo group bonded to a benzene ring through a linking group) is added to the optically anisotropic layer to control the tilt angle of the discotic liquid crystalline compound. It has been proposed (see, for example, Patent Document 4). Furthermore, a method for controlling the orientation of a liquid crystal compound by using a hydrophobic excluded volume effect compound in combination with an optically anisotropic layer has been proposed (see, for example, Patent Document 5).

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 film that copes with uneven light leakage in response to an increase in size and brightness. Although a technique for improving unevenness by incorporating a leveling agent into a polymerizable liquid crystal has been disclosed (for example, Patent Document 6), it is effective only when the polymerizable liquid crystal is homogeneously aligned, as in the present invention. It has been found that it cannot be applied to complicated orientations including hybrid orientation.
US Pat. No. 5,583,679 US Pat. No. 5,646,703 JP-A-8-95030 JP 2001-330725 A JP 2002-20363 A JP-A-11-148080

  When the present inventors actually used the above-mentioned optical compensation sheet for a liquid crystal display device, light leakage from an oblique direction was recognized or the viewing angle was sufficiently widened by the combination with the polarizing plate of the liquid crystal display device. The optical compensation function was not sufficient. One reason for the insufficient optical compensation function is that the liquid crystalline molecules of the optically anisotropic layer could not be aligned with a sufficiently large tilt angle. On the other hand, in the manufacture, the liquid crystal composition is heated and aligned to achieve monodomain hybrid alignment. For this reason, if the ripening time is shortened for the purpose of manufacturing efficiency, there is a problem that the occurrence of orientation defects tends to become remarkable, and it is necessary to develop a technique that can shorten the monodomainization time. In particular, when the cellulose partial esterified product is added to increase the tilt angle on the air interface side in order to obtain the desired optical performance, the viscosity of the liquid crystal composition is increased, and the defect disappearance rate is significantly delayed. It will cause extreme inefficiency. Therefore, there has been a strong demand for the development of an air interface side tilt angle control technique that does not hinder the disappearance of surface alignment defects.

  In view of the above-described problems, the present invention provides an optical compensation sheet having an optically anisotropic layer exhibiting optical anisotropy expressed by hybrid alignment of liquid crystalline molecules. It is an object to provide a novel optical compensation sheet having an excellent optical compensation function by increasing the tilt angle. In particular, an optical element that contributes to improving the viewing angle of a liquid crystal display device such as a TN mode or an OCB mode, which has an optically anisotropic layer formed from a discotic liquid crystal compound that is hybrid-aligned by increasing the tilt angle on the air interface side. It is an object to provide a compensation sheet. In particular, an object of the present invention is to provide an optical compensation sheet that contributes to display of an image with high display quality without causing unevenness even in a large-sized liquid crystal display device.

Means for solving the above problems are as follows.
[1] 1 selected from the group consisting of a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. A composition comprising at least one kind of a polymer containing a hydrophilic group of at least one kind in a side chain and a liquid crystalline compound.
[2] The composition according to [1], wherein the polymer is a copolymer including a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1).

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、水素原子または置換基を表し；Ｌは下記の連結基群から選ばれる２価の連結基または下記の連結基群から選ばれる２つ以上を組み合わせて形成される２価の連結基を表し、
（連結基群）
単結合、−Ｏ−、−ＣＯ−、−ＮＲ⁴−（Ｒ⁴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）（ＯＲ⁵）（Ｒ⁵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；
Ｑはカルボキシル基（−ＣＯＯＨ）もしくはその塩、スルホ基（−ＳＯ₃Ｈ）もしくはその塩、またはホスホノキシ基｛−ＯＰ（＝Ｏ）（ＯＨ）₂｝もしくはその塩を表す。）
［３］ 前記液晶性化合物が、ディスコティック液晶性化合物である前記［１］又は［２］に記載の組成物。
［４］ 前記ディスコティック液晶性化合物が、トリフェニレン液晶である前記［３］に記載の組成物。
［５］ 前記ポリマーが、４０質量％以上のフルオル脂肪族基含有モノマーを有する前記［１］〜［４］のいずれか一項に記載の組成物。
［６］ 前記ポリマーの質量平均分子量が、１０万以下である前記［１］〜［５］のいずれか一項に記載の組成物。

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent; L is selected from a divalent linking group selected from the following linking group group or the following linking group group: Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group) —, an alkylene group, and an arylene group;
Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. )
[3] The composition according to [1] or [2], wherein the liquid crystalline compound is a discotic liquid crystalline compound.
[4] The composition according to [3], wherein the discotic liquid crystalline compound is a triphenylene liquid crystal.
[5] The composition according to any one of [1] to [4], wherein the polymer has 40% by mass or more of a fluoroaliphatic group-containing monomer.
[6] The composition according to any one of [1] to [5], wherein the polymer has a mass average molecular weight of 100,000 or less.

[7] Any one of [1] to [6], further comprising at least one polymer including a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following general formula (A): A composition according to claim 1.

上記一般式（Ａ）において、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のアルキル基を表し、好ましくは水素原子またはメチル基である。）、Ｈ^fは水素原子またはフッ素原子を表し、ｍは１以上６以下の整数、ｎは２〜４の整数を表す。

In the above general formula (A), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — (R ¹² is a hydrogen atom or an alkyl having 1 to 4 carbon atoms). Represents a group, preferably a hydrogen atom or a methyl group.), H ^f 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.

[8] The polymer containing a repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A) further contains at least one repeating unit derived from the monomer represented by the following general formula (B). The composition according to [7] above.

上記一般式（Ｂ）において、Ｒ⁶は水素原子またはメチル基を表し、Ｚは２価の連結基を表し、Ｒ⁷は置換基を有しても良いポリ（アルキレンオキシ）基または置換基を有しても良い炭素数１以上２０以下の直鎖、分岐鎖または環状のアルキル基を表す。

In the general formula (B), R ⁶ represents a hydrogen atom or a methyl group, Z represents a divalent linking group, and R ⁷ represents a poly (alkyleneoxy) group or a substituent which may have a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may be present.

[9] An optical compensation sheet having an optically anisotropic layer formed from the composition according to any one of [1] to [8].
[10] The liquid crystalline compound contained in the composition is a discotic liquid crystalline compound, and the tilt angle θ1 of the liquid crystalline molecules at one interface of the optically anisotropic layer satisfies 0 ° ≦ θ1 ≦ 30 °. The optical compensation sheet according to [9], wherein the optical compensation sheet is satisfied and the tilt angle θ2 of the other interface satisfies 50 ° ≦ θ2.
[11] Formed from a liquid crystalline compound fixed in an alignment state, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ } and an optically compensatory sheet having an optically anisotropic layer containing at least one polymer having a side chain of one or more hydrophilic groups selected from the group consisting of salts thereof.
[12] Formed from a liquid crystalline compound fixed in an aligned state, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ } and a liquid crystal display device having an optically anisotropic layer containing at least one polymer having a side chain of one or more hydrophilic groups selected from the group consisting of salts thereof.
[13] Formed from a liquid crystalline compound fixed in an aligned state, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ } and an elliptically polarizing plate having an optically anisotropic layer containing at least one polymer having a side chain containing one or more hydrophilic groups selected from the group consisting of salts thereof and a linearly polarizing film.
[14] The optical compensation according to [11], wherein the optically anisotropic layer further contains at least one polymer containing a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following general formula (A). A sheet, the liquid crystal display device according to [12], or the elliptically polarizing plate according to [13].

上記一般式（Ａ）において、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のアルキル基を表し、好ましくは水素原子またはメチル基である。）、Ｈ^fは水素原子またはフッ素原子を表し、ｍは１以上６以下の整数、ｎは２〜４の整数を表す。

In the above general formula (A), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — (R ¹² is a hydrogen atom or an alkyl having 1 to 4 carbon atoms). Represents a group, preferably a hydrogen atom or a methyl group.), H ^f 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.

[15] The polymer including a repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A) further includes at least one repeating unit derived from the monomer represented by the following general formula (B). The optical compensation sheet, the liquid crystal display device or the elliptically polarizing plate as described in [14] above.

上記一般式（Ｂ）において、Ｒ⁶は水素原子またはメチル基を表し、Ｚは２価の連結基を表し、Ｒ⁷は置換基を有しても良いポリ（アルキレンオキシ）基または置換基を有しても良い炭素数１以上２０以下の直鎖、分岐鎖または環状のアルキル基を表す。

In the general formula (B), R ⁶ represents a hydrogen atom or a methyl group, Z represents a divalent linking group, and R ⁷ represents a poly (alkyleneoxy) group or a substituent which may have a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may be present.

  In the present invention, “hybrid alignment” means the major axis direction of liquid crystalline molecules (for example, the disk surface of the core in the case of discotic liquid crystal molecules) and the horizontal plane of the optically anisotropic layer (in the present invention, optically anisotropic). Since the conductive layer is formed on the support via the alignment film, the angle (hereinafter referred to as “tilt angle”) with the surface of the support increases with the distance from the support, that is, optically anisotropic. Refers to an orientation that changes in the thickness direction of the optical layer, and includes two interfaces of the optical anisotropic layer (for example, when the optical anisotropic layer is formed on the alignment film, When the optically anisotropic layer is once formed and then placed on another support by transfer or the like, the two interfaces are not necessarily the alignment film interface and the air interface). Realized by liquid crystalline molecules with different orientations at different anglesWhen the optically anisotropic layer is formed on the alignment film, the liquid crystal has different tilt angles between the optically anisotropic layer / alignment film interface and the optically anisotropic layer / air interface that is also the outermost surface of the optical compensation sheet. Realized by sex molecules. In the present invention, the aspect of change in tilt angle includes continuous increase, continuous decrease, intermittent increase, intermittent decrease, change including continuous increase and continuous decrease, and intermittent change including increase and decrease, etc. Both shall be included. The intermittent change includes a region where the tilt angle does not change in the middle of the thickness direction. In the “hybrid orientation” in the present invention, it is preferable that the overall increase or decrease is included even if the tilt angle does not change. Further, it is preferable that the tilt angle as a whole increases with the distance from the support, and it is particularly preferable that the tilt angle change continuously.

  In the present invention, by forming an optically anisotropic layer from a liquid crystalline composition containing a fluoropolymer, the tilt angle of the air interface of the liquid crystalline molecule is controlled, and the monodomainization time of the alignment of the liquid crystalline molecule is reduced. By shortening, it is possible to produce an optically anisotropic layer and thus an optical compensation sheet with high efficiency. The optical compensation sheet of the present invention contributes to the expansion of the viewing angle of the liquid crystal display device when applied to an image display device. Further, according to the present invention, by using a liquid crystal compound and a fluorine-based polymer in combination, an image with high display quality can be displayed without causing unevenness. Furthermore, applicability such as repelling is improved.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
The present invention includes a liquid crystalline compound, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. The present invention relates to a composition containing at least one polymer having a side chain containing one or more hydrophilic groups selected from the group consisting of: For example, the composition of the present invention is applied onto an alignment film to align liquid crystal compound molecules in the presence of the fluoroaliphatic group-containing polymer (hereinafter sometimes abbreviated as “fluorine polymer”). As a result, the liquid crystalline molecules can be aligned with a large tilt angle, particularly at the air interface with a large tilt angle. As a result, it is possible to stably form an optically anisotropic layer expressed by hybrid alignment of liquid crystalline molecules. Furthermore, by containing at least one polymer containing a repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A), coating properties such as unevenness and repellency are improved. Hereinafter, each material used in the present invention will be described in detail.
In the present specification, the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.

[Fluoropolymer]
First, one kind selected from the group consisting of a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof The fluoroaliphatic group-containing polymer containing the above hydrophilic group will be described in detail. The types of polymers are described in “Revised Chemistry of Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., 1968), pages 1-4, for example, polyolefins, polyesters, polyamides, polyimides. , Polyurethanes, polycarbonates, polysulfones, polycarbonates, polyethers, polyacetals, polyketones, polyphenylene oxides, polyphenylene sulfides, polyarylates, PTFEs, polyvinylidene fluorides, cellulose derivatives, etc. It is done. The fluoropolymer is preferably a polyolefin.

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

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

  For the production of the fluoropolymer of the present invention, a fluoroaliphatic group-containing monomer represented by the following general formula (A1) is preferably used.

In the above general formula (A1), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — (R ¹² is a hydrogen atom or an alkyl having 1 to 4 carbon atoms). Represents a group, preferably a hydrogen atom or a methyl group.), H ^f 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.

X is preferably an oxygen atom, ^Hf is preferably a hydrogen atom, m is preferably 1 or 2, n is preferably 3 or 4, and a mixture thereof may be used.

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

  One aspect of the fluoropolymer usable in the present invention is a copolymer having a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit containing a hydrophilic group represented by the following general formula (1). It is a polymer.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent. Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. L represents an arbitrary group selected from the following linking group group, or a divalent linking group formed by combining two or more thereof.
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group.

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

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

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

R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), or a group represented by -LQ described later. It is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom, or a group represented by -LQ, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is particularly preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, most preferably R ² and R ³ are hydrogen atoms, and R ¹ is a hydrogen atom or a methyl group. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group and the like. The alkyl group may have a suitable substituent. Examples of the substituent include a halogen atom, aryl group, heterocyclic group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxyl group, acyloxy group, amino group, alkoxycarbonyl group, acylamino group, oxycarbonyl Group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, sulfolyl group, carboxyl group and the like. The carbon number of the alkyl group does not include the carbon atom of the substituent. The same applies to the carbon number of other groups.

L represents a divalent linking group selected from the above linking group group, or a divalent linking group formed by combining two or more thereof. In the linking group group, R ^{4 in} —NR ⁴ — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom or an alkyl group. R ⁵ in —PO (OR ⁵ ) — represents an alkyl group, an aryl group or an aralkyl group, and preferably an alkyl group. When R ⁴ and R ⁵ represent an alkyl group, an aryl group or an aralkyl group, the number of carbon atoms is the same as that described in the “Substituent group”. L preferably contains a single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, an alkylene group or an arylene group, and is a single bond, —CO—, —O—. , —NR ⁴ —, an alkylene group or an arylene group is particularly preferable, and a single bond is most preferable. When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of particularly preferred alkylene groups include methylene, ethylene, trimethylene, tetrabutylene, hexamethylene groups and the like. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene and naphthalene groups. When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 34, more preferably 7 to 26, and particularly preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group. The group listed as L may have a suitable substituent. Examples of such a substituent include those similar to the substituents exemplified above as the substituents for R ^{1 to} R ³ .
Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

  In the formula (1), Q is a carboxyl group, a salt of a carboxyl group (for example, lithium salt, sodium salt, potassium salt, ammonium salt (for example, ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, trimethyl). Benzylammonium, dimethylphenylammonium, etc.), pyridinium salts, etc.), sulfo groups, salts of sulfo groups (examples of cations forming salts are the same as those described above for carboxyl groups), phosphonoxy groups, salts of phosphonoxy groups (salts) Examples of the cation that forms are the same as those described above for the carboxyl group). A carboxyl group, a sulfo group, and a phospho group are more preferable, a carboxyl group or a sulfo group is particularly preferable, and a carboxyl group is most preferable.

  Specific examples of the monomer corresponding to the formula (1) that can be used in the production of the fluoropolymer usable in the present invention are listed below, but the present invention is not limited to the following specific examples.

  The fluoropolymer may contain one type of repeating unit represented by the general formula (1) or two or more types. Moreover, the said fluorine-type polymer may have 1 type (s) or 2 or more types of repeating units other than said each repeating unit. The other repeating units are not particularly limited, and preferred examples thereof include repeating units derived from ordinary radical polymerizable monomers. Hereinafter, specific examples of monomers for deriving other repeating units will be given. The fluoropolymer may contain a repeating unit derived from one or 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 Methoxypolyethylene glycol methacrylate (number of added polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate Glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc .;

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

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

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

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

  As the monomer that does not have a fluoroaliphatic group and derives another repeating unit, a monomer represented by the following general formula (B1) is preferably used.

In the general formula (B1), R ⁶ represents a hydrogen atom or a methyl group, Z represents a divalent linking group, and R ⁷ represents a poly (alkyleneoxy) group or a substituent which may have a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may be present. 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 methyl, ethyl, propyl or butyl. R ⁵ is more preferably a hydrogen atom or methyl. Y is particularly preferably an oxygen atom, —NH—, or —N (CH ₃ ) —.

In the above general formula (B1), the poly (alkyleneoxy) group can be represented by (RO) _x , and R is an alkylene group having 2 to 4 carbon atoms, such as —CH ₂ CH ₂ —, —CH _2. It is preferably CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, or —CH (CH ₃ ) CH (CH ₃ ) —.
The alkyleneoxy units in the poly (alkyleneoxy) group may be the same in all units such as poly (propyleneoxy), and two or more different alkyleneoxy units are randomly distributed. (For example, a linear propyleneoxy unit, a branched propyleneoxy unit and an ethyleneoxy unit are randomly distributed), or a combination of two or more different alkyleneoxy unit blocks ( For example, a linear or branched block of propyleneoxy units and a block of ethyleneoxy units may be combined).
In this poly (alkyleneoxy) chain, a plurality of poly (alkyleneoxy) units are one or more linking groups (for example, -CONH-Ph-NHCO-, -S-, etc., where Ph represents a phenylene group) ) Can be included. When the linking group has a valence of 3 or more, a branched alkyleneoxy unit can be obtained thereby. When this copolymer is used in the present invention, the molecular weight of the poly (alkyleneoxy) group is suitably from 250 to 3,000.

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, and a hexyl group, which may be linear or branched. Monocyclic cycloalkyl groups such as cyclohexyl group and cycloheptyl group And polycyclic cycloalkyl groups such as a bicycloheptyl group, a bicyclodecyl group, a tricycloundecyl group, a tetracyclododecyl group, an adamantyl group, a norbornyl group, and a tetracyclodecyl group are preferably used.

Examples of the substituent of the poly (alkyleneoxy) group or 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, Examples include, but are not limited to, halogen atoms such as chlorine atom and bromine atom, nitro group, cyano group and amino group.

  The monomer represented by the general formula (B1) is particularly preferably alkyl (meth) acrylate or poly (alkyleneoxy) (meth) acrylate.

  Specific examples of the monomer represented by the general formula (B1) are shown below, but the present invention is not limited to the following specific examples.

Poly (alkyleneoxy) acrylate and methacrylate are commercially available hydroxypoly (alkyleneoxy) materials such as “Pluronic” (Pluronic (Asahi Denka Kogyo Co., Ltd.)), “Adeka Polyether” (Asahi Denka Kogyo ( “Carbowax” [Carbowax (Glyco Product)], “Triton” [Toriton (Rohm and Haas) and “PEG” (Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by reacting what is sold as)) with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride in a known manner.
Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  In the fluoropolymer, the amount of the fluoroaliphatic group-containing monomer is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 30% by mass or more of the total amount of constituent monomers of the polymer. Is more preferable. In the fluoropolymer, the amount of the repeating unit represented by the general formula (1) is preferably 1% by mass or more, more preferably 2 to 20% by mass of the total amount of the constituent monomers of the fluoropolymer. It is particularly preferably 2 to 10% by mass, and most preferably 2 to 5% by mass.

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

  The polymerization method employed when producing the fluoropolymer is not particularly limited, but for example, a polymerization method such as cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group may be adopted. Among these, radical polymerization is particularly preferable 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 peroxide (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 are: alcohols such as isopropanol and butanol; ethers such as dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate and acetic acid And esters such as butyl, amyl acetate, and γ-butyrolactone; and aromatic hydrocarbons such as benzene, toluene, and xylene. 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 and the like, and must be precisely controlled. It is about 01 mol% to 50 mol%, preferably 0.05 mol% to 30 mol%, particularly preferably 0.08 mol% to 25 mol%. These chain transfer agents may be present in the system simultaneously with the target monomer whose degree of polymerization is to be controlled in the polymerization process, and the addition method is not particularly limited. It may be added after being dissolved in the monomer, or may be added separately from the monomer.

  Specific examples of the fluoroaliphatic group-containing copolymer preferably used in the present invention as a fluorine-based polymer 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.

  The composition of this invention may contain 2 or more types of the said fluoropolymer. In addition, the composition of the present invention preferably contains a polymer containing a fluoroaliphatic group together with the fluorine-based polymer. Among them, a fluoroaliphatic group-containing compound represented by the following general formula (A) is preferable. A polymer containing at least one repeating unit derived from a monomer is preferred.

In the above general formula (A), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — (R ¹² is a hydrogen atom or an alkyl having 1 to 4 carbon atoms). Represents a group, preferably a hydrogen atom or a methyl group.), H ^f 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.

  The preferable range of the said general formula (A) is the same as the preferable range of the said general formula (A1), and F1-F70 can be mentioned as a specific example.

  Furthermore, the polymer containing the repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A) may contain at least one repeating unit derived from the monomer represented by the following general formula (B). preferable.

In the general formula (B), R ⁶ represents a hydrogen atom or a methyl group, Z represents a divalent linking group, and R ⁷ represents a poly (alkyleneoxy) group or a substituent which may have a substituent. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may be present.

  The preferable range of the said general formula (B) is the same as the preferable range of the said general formula (B1), and A1-A150 can be mentioned as a specific example.

The polymer containing a repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A) includes a repeating unit derived from the monomer represented by the general formula (A) and the general formula (B). Two or more kinds may be contained, and repeating units other than these may be contained. Specific examples of other repeating units include repeating units derived from monomers selected from the monomer groups (1) to (8).
Specific examples of the polymer containing a repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A) are shown below, but the present invention is not limited to the following specific examples.

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

  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 0.2 to 2.5% by mass is even more preferable. If the addition amount of the fluorine-based polymer is less than 0.005% by mass, the effect is insufficient, and if it exceeds 8% by mass, the coating film cannot be sufficiently dried, or the performance as an optical film (for example, letter The uniformity of the foundation). When the polymer containing a repeating unit derived from the fluoroaliphatic group-containing monomer represented by the general formula (A) is contained, the content of the polymer is 0.1 to 1. It is preferably 5% by mass, more preferably 0.1 to 1.0% by mass. When the content is in the above range, unevenness or repelling at the time of application can be further reduced.

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

[Liquid crystal compounds]
In the present invention, as the liquid crystalline compound, any of a rod-like liquid crystalline compound and a discotic liquid crystalline compound may be used, and either a high molecular liquid crystal or a low molecular liquid crystal may be used. Furthermore, after forming the optically anisotropic layer using the composition of the present invention, for example, the low molecular liquid crystal may be contained in a crosslinked state in the optically anisotropic layer, and may no longer exhibit liquid crystallinity. . As the liquid crystalline compound used in the present invention, a discotic liquid crystalline compound is preferable.

  Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. The rod-like liquid crystal compound includes a metal complex liquid crystal compound. Moreover, the liquid crystal polymer which contains a rod-shaped liquid crystalline compound in a repeating unit can also be used as a rod-shaped liquid crystalline compound. In other words, the rod-like liquid crystalline compound may be bonded to a (liquid crystal) polymer. For rod-like liquid crystalline compounds, see Chapter 4, Chapter 7 and Chapter 11 of the Chemistry of the Quarterly Chemical Review Vol. 22 Liquid Crystal Chemistry (1994) edited by the Chemical Society of Japan, and the 142nd Committee of the Japan Society for the Promotion of Science. Described in Chapter 3. The birefringence of the rod-like liquid crystalline compound is preferably in the range of 0.001 to 0.7. The rod-like liquid crystalline compound preferably has a polymerizable group in order to fix its alignment state. The rod-like liquid crystalline compound is described in WO01 / 88574A1, page 50, line 7 to page 57, last line.

  Examples of discotic liquid crystalline compounds include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles. Further, the discotic liquid crystal compounds generally have a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain. Is also included and exhibits liquid crystallinity. Preferred examples of the discotic liquid crystalline compound are described in JP-A-8-50206.

  As the liquid crystalline compound used in the present invention, triphenylene liquid crystal is particularly preferable. Examples of the triphenylene liquid crystal used in the present invention include the C.I. Destrade et al., Mol. Cryst. 71, 111 (1981); Mourey et al., Mol. Cryst. 84, 193 (1982), and the like. Particularly preferred triphenylene liquid crystals are triphenylene derivatives represented by general formulas (1) to (3) described in JP-A-7-306317, and general formula (I) described in JP-A-7-309813. And triphenylene derivatives represented by the general formula (I) described in JP-A-2001-100028.

  In addition, when the optically anisotropic layer is finally formed, the liquid crystal compound no longer needs to be a liquid crystal compound. For example, a low molecular weight discotic liquid crystalline compound has a group that reacts with heat, light, etc., and as a result, polymerizes or crosslinks by reaction with heat, light, etc. Also good. The polymerization of the discotic liquid crystalline compound is described in JP-A-8-27284, and can be applied to the present invention.

  As an example of a method for fixing a discotic liquid crystalline compound by polymerization, as a discotic liquid crystalline compound, a liquid crystalline compound having a polymerizable group bonded as a substituent to a discotic core is used for hybrid alignment, and then the liquid crystalline There is a method of polymerizing and fixing a compound. However, when a polymerizable group is directly connected to the discotic core, it tends to be difficult to maintain the alignment state in the polymerization reaction. Therefore, it is preferable to introduce a linking group between the discotic core and the polymerizable group. As a preferable discotic liquid crystalline compound having a polymerizable group, a compound represented by the following formula (2) may be mentioned.

General formula (2)
D (-LP) _n
In the formula, D represents a discotic core, L represents a divalent linking group, P represents a polymerizable group, and n represents an integer of 2 to 12. Specific examples of the discotic liquid crystalline compound are described in WO01 / 88574A1 on page 58, line 6 to page 65, line 8.

  As the most preferable liquid crystal compound used in the present invention, triphenylene derivatives represented by general formulas (1) to (3) described in JP-A-7-306317, and general formulas described in JP-A-7-309813. Among the triphenylene derivatives represented by (I) and the triphenylene derivatives represented by the general formula (I) described in JP-A-2001-100028, compounds having a linking group between the triphenylene core and the polymerizable group are used. Can be mentioned.

  In the present invention, two or more kinds of liquid crystal compounds may be used in combination. Further, for example, the polymerizable discotic liquid crystalline compound and the non-polymerizable discotic liquid crystalline compound can be used in combination. The non-polymerizable discotic liquid crystalline compound is preferably a compound in which the polymerizable group (P in the formula (2)) of the polymerizable discotic liquid crystalline compound described above is changed to a hydrogen atom or an alkyl group. That is, the non-polymerizable discotic liquid crystalline compound is preferably a compound represented by the following formula (3).

General formula (3)
D (-LR) _n
In the formula, D represents a discotic core, L represents a divalent linking group, R represents a hydrogen atom or an alkyl group, and n is an integer of 4 to 12.

[Additive for optically anisotropic layer]
When forming an optically anisotropic layer using the composition of this invention, arbitrary additives can be used together with the said liquid crystalline compound and the said fluorine-type polymer in the said composition. Examples of additives include an anti-repellent agent, an additive for controlling the tilt angle of the alignment film (tilt angle of the liquid crystalline compound at the optically anisotropic layer / alignment film interface), a polymerization initiator, and an alignment temperature. Additives (plasticizers) to be reduced, polymerizable monomers, and the like. Hereinafter, for each additive,

[Anti-repellent agent]
As a material for use in combination with a liquid crystal compound, particularly a discotic liquid crystal compound, to prevent repelling at the time of coating, a polymer compound can generally be suitably used. The polymer to be used is not particularly limited as long as it is compatible with the liquid crystal compound and does not significantly inhibit the tilt angle change or orientation of the liquid crystal compound. Examples of polymers that can be used as repellency inhibitors are described in JP-A-8-95030, and particularly preferred specific polymer examples include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. In order not to inhibit the alignment of the liquid crystalline compound, the amount of the polymer used for the purpose of preventing repellency is generally preferably in the range of 0.1 to 10% by mass with respect to the liquid crystalline compound. More preferably, it is in the range of 8% by mass, and even more preferably in the range of 0.1-5% by mass.

[Alignment film tilt angle control agent]
As an additive for controlling the tilt angle of the alignment film, a compound having both a polar group and a nonpolar group in the molecule can be added. Examples of the compound having a polar group include R—OH, R—COOH, R—O—R, R—NH ₂ , R—NH—R, R—SH, R—S—R, R—CO—R, R -COO-R, R-CONH- R, R-CONHCO-R, R-SO 3 H, R-SO 3 -R, R-SO 2 NH-R, R-SO 2 NHSO 2 -R, R-C = N-R, HO-P (-OR) 2, (HO-) 2 P-OR, P (-OR) 3, HO-PO (-OR) 2, (HO-) 2 PO-OR, PO ( -OR) ₃ , R-NO ₂ , R-CN, and the like. Moreover, organic salts (for example, ammonium salt, pyridinium salt, carboxylate, sulfonate, phosphate) may be used. Among the compounds having the polar group, R—OH, R—COOH, R—O—R, R—NH ₂ , R—SO ₃ H, HO—PO (—OR) ₂ , (HO—) ₂ PO— OR, PO (—OR) ₃ or organic salts are preferred. Here, each R above represents a nonpolar group, for example, an alkyl group (preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably 1 carbon atom). -30 linear, branched, cyclic substituted or unsubstituted alkenyl group), alkynyl group (preferably a linear, branched, cyclic substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms), aryl group (preferably Examples thereof include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms). These nonpolar groups may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group). Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonyl Mino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group And carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like.

  Adjusting the tilt angle of liquid crystal molecules at the alignment film side interface by adding an alignment film tilt control agent to the composition of the present invention and orienting the molecules of the liquid crystalline compound in the presence of the alignment film tilt control agent However, the amount of change at that time is related to the rubbing density. If an alignment film having a high rubbing density is compared with an alignment film having a low rubbing density, the tilt angle is more likely to change in the alignment film having a low rubbing density even if the amount of the alignment film tilt control agent added is the same. Therefore, the preferred range of the added amount of the alignment film tilt control agent varies depending on the rubbing density of the alignment film to be used, the desired tilt angle, and the like. The content is preferably 0001% by mass to 30% by mass, more preferably 0.001% by mass to 20% by mass, and still more preferably 0.005% by mass to 10% by mass. Specific examples of the alignment film tilt control agent that can be used in the present invention are shown below, but the present invention is not limited to the following specific examples.

[Polymerization initiator]
It is preferable to form an optically anisotropic layer by fixing the molecules of the liquid crystalline compound in an aligned state, and it is preferable to fix the molecules of the liquid crystalline compound by utilizing a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. In order to prevent deformation of the support and the like due to heat, the photopolymerization reaction is performed. preferable. Examples of the photopolymerization initiator, the amount of photopolymerization initiator used, and the value of the light irradiation energy for polymerization are described in paragraphs [0050] to [0051] of JP-A No. 2001-91741 in the present invention. Applicable.

[Polymerizable monomer]
A polymerizable monomer may be used together with the liquid crystal compound. The polymerizable monomer that can be used in the present invention is not particularly limited as long as it is compatible with the liquid crystal compound and does not cause a significant change in tilt angle or inhibition of alignment of the liquid crystal compound. Among these, compounds having a polymerization active ethylenically unsaturated group such as a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloyl group are preferably used. The addition amount of the polymerizable monomer is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the liquid crystal compound. In addition, it is particularly preferable to use a monomer having two or more reactive functional groups because an effect of improving the adhesion between the alignment film and the optically anisotropic layer can be expected.

[Coating solvent]
The composition of the present invention may be prepared as a coating solution. As a solvent used for preparation of a coating liquid, an organic solvent is preferable. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Application method]
Application of the coating liquid to the alignment film surface can be performed by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method). Moreover, 1-50 mass% is preferable, as for content of the liquid crystalline compound in a coating liquid, 10-50 mass% is more preferable, and 20-40 mass% is more preferable.

[Characteristics of optically anisotropic layer]
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.

  When the composition of the present invention is applied onto the alignment film, the liquid crystalline molecules are aligned at the tilt angle of the alignment film at the interface with the alignment film and at the tilt angle of the air interface at the interface with air. After applying the composition of the present invention to the surface of the alignment film, the liquid crystal compound is uniformly aligned (monodomain alignment). The tilt angle of the liquid crystalline compound (angle formed by the normal of the disc surface of the discotic liquid crystalline compound and the normal of the surface on which the alignment layer of the transparent support is provided) changes continuously in the depth direction of the anisotropic layer. Hybrid orientation can be realized. An optical compensation sheet having an optically anisotropic layer formed by hybrid-aligning liquid crystal molecules and fixing the liquid crystal molecules in the alignment state contributes to an increase in the viewing angle of a liquid crystal display device, and a decrease in contrast to a change in viewing angle. This contributes to preventing gradation or black / white inversion, hue change, and the like.

  In the presence of the fluorinated polymer, the liquid crystal molecules can be aligned at a tilt angle of 50 ° or more at the air interface. In order to realize hybrid alignment in a state where preferable performance can be exhibited as an optical compensation sheet, the tilt angle of the liquid crystalline molecules on the alignment film side is preferably 3 ° to 30 °. The tilt angle of the liquid crystal molecules on the alignment film side can be controlled by the above-described methods (alignment film rubbing density, alignment film tilt angle control agent, etc.). On the other hand, the tilt angle of the liquid crystal molecules on the air interface side is formed by using the fluorine-based polymer and other compounds added as desired (for example, at least two kinds of compounds having the hydrogen bonding group). And a preferred hybrid alignment state can be realized depending on the display mode of the liquid crystal display device to which the optical compensation sheet of the present invention is applied.

[Tilt angle]
The tilt angle refers to an angle formed between the major axis direction of the molecule of the liquid crystal compound and the normal line of the interface (alignment film interface or air interface). In the present invention, the tilt angle of the alignment film is 3 ° to 30 °, air The tilt angle on the interface side is preferably 40 to 80 °. If the tilt angle of the alignment film is too small, the time required for monodomain alignment of the liquid crystal compound, particularly the discotic liquid crystal compound, is increased, but a larger value is preferable. However, if the tilt angle is too large, the optical compensation sheet On the contrary, it is not preferable because preferable optical performance cannot be obtained. Therefore, from the viewpoint of shortening the monodomain formation time and preferable optical performance as an optical compensation sheet, the tilt angle of the preferred alignment film is preferably 5 ° to 30 °, more preferably 10 to 30 °, and particularly preferably 20 to. 30 °. Further, the tilt angle on the air interface side is preferably 40 to 80 °, more preferably 50 to 80 °, and particularly preferably 50 to 70 °. The tilt angle on the alignment film side can be controlled in the range of several degrees to several tens of degrees by changing the rubbing density of the alignment film or adding the alignment film tilt angle control agent. As described above, when the optically anisotropic layer is once formed and then disposed between two layers by transfer or the like, the interface of the optically anisotropic layer is not necessarily the alignment film interface and the air interface. In such an embodiment, the tilt angle of the liquid crystalline molecules on one interface side and the other interface side of the two interfaces of the optically anisotropic layer is such that the alignment film side tilt angle range and the air interface side The tilt angle is preferably in the range.

[Alignment film]
The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. As long as the desired orientation can be imparted to the liquid crystalline compound of the optically anisotropic layer provided on the alignment film, any layer may be used as the alignment film. In the present invention, the tilt angle of the alignment film is controlled. From the viewpoint of easiness, an alignment film formed by a rubbing treatment of a polymer is particularly preferable. The rubbing treatment can be generally carried out by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. In particular, in the present invention, it is described in “Liquid Crystal Handbook” (Maruzen Co., Ltd.). It is preferable to carry out by a method. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.05 to 1 μm. The polymer used for the alignment film is described in many documents, and many commercially available products can be obtained. In the alignment film for an optical compensation film of the present invention, polyvinyl alcohol and derivatives thereof are preferably used. Particularly preferred is a modified polyvinyl alcohol having a hydrophobic group bonded thereto. Regarding the alignment film, reference can be made to the description of page 43, line 24 to page 49, line 8 of WO01 / 88574A1.

[Rubbing density of alignment film]
As a method for changing the rubbing density of the alignment film, a method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd.) can be used. The rubbing density (L) is quantified by the formula (A).
Formula (A) L = Nl {1+ (2πrn / 60v)}
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed). In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can reverse this. Between the rubbing density and the tilt angle of the alignment film, there is a relationship in which the tilt angle decreases as the rubbing density increases and the tilt angle increases as the rubbing density decreases.

  If the liquid crystal molecules are aligned and the state is fixed by polymerization or the like, the alignment state can be maintained without an alignment film. Therefore, after the optically anisotropic layer is formed on an alignment film (for example, an alignment film formed on a temporary support), only the optically anisotropic layer is transferred onto the transparent support. An optical compensation sheet can also be produced. That is, the present invention includes an aspect of an optical compensation sheet that does not include an alignment film.

[Transparent support]
The support used in the present invention is preferably transparent, and the light transmittance is preferably 80% or more. It is preferable to use an optically isotropic polymer film. As the specific examples and preferred embodiments of the polymer, the description in paragraph [0013] of JP-A-2002-22294 can be applied. In addition, even a conventionally known polymer such as polycarbonate or polysulfone, which easily develops birefringence, should have a decreased expression by modifying the molecule described in WO00 / 26705. You can also.

  As the polymer film, it is preferable to use cellulose acetate having an acetylation degree of 55.0 to 62.5%. In particular, the acetylation degree is preferably 57.0 to 62.0%. The description of paragraph number [0021] of JP-A No. 2002-196146 can be applied to the degree of acetylation, the range thereof, and the chemical structure of cellulose acetate. About manufacturing a cellulose acylate film using a non-chlorinated solvent, it is described in detail in JIII Journal of Technical Disclosure No. 2001-1745, and the cellulose acylate film described therein is also preferably used in the present invention. it can.

  The description of paragraph numbers [0018] to [0019] of JP-A No. 2002-139621 can be applied to the retardation value in the thickness direction of the cellulose ester film used as the transparent support and the range of the birefringence.

  In order to adjust the retardation of a polymer film used as a transparent support, particularly a cellulose acylate film, it is preferable to use an aromatic compound having at least two aromatic rings as a retardation increasing agent. The description of paragraph numbers [0021] to [0023] of JP-A No. 2002-139621 can be applied to the preferred range and usage amount of the aromatic compound. Such retardation increasing agents are described in WO01 / 88574A1, WO00 / 2619A1, JP-A Nos. 2000-1111914, 2000-275434, and Japanese Patent Application No. 2002-70009.

  The cellulose acylate film is preferably produced by a solvent cast method from the prepared cellulose acylate solution (dope). It is preferable to add the above-mentioned retardation increasing agent to the dope. Using the prepared cellulose acylate solution (dope), a film can be formed by casting two or more layers of the dope. The description of paragraph numbers [0038] to [0040] of JP-A No. 2002-139621 can be applied to the formation of the film.

  The retardation of the cellulose acylate film can be further adjusted by a stretching treatment. The draw ratio is preferably in the range of 3 to 100%. When stretching the cellulose acylate film, tenter stretching is preferably used, and in order to control the slow axis with high accuracy, it is preferable to make the difference between the left and right tenter clip speeds, the separation timing, etc. as small as possible. .

  A plasticizer can be added to the cellulose ester film in order to improve mechanical properties or increase the drying speed. As a plasticizer, the aspect of paragraph number [0043] of JP, 2002-139621, A and a desirable range are applicable to the present invention.

  Degradation inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines) and UV inhibitors may be added to the cellulose ester film. Regarding the deterioration preventing agent, the description in paragraph number [0044] of JP-A No. 2002-139621 can be applied. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. The ultraviolet ray preventing agent is described in JP-A-7-11056.

  Regarding the surface treatment of the cellulose acylate film and the surface energy of the solid, the description in paragraph numbers [0051] to [0052] of JP-A No. 2002-196146 can be applied.

  The thickness of the cellulose acylate film varies depending on the purpose of use, but is usually in the range of 5 to 500 μm, more preferably in the range of 20 to 250 μm, and most preferably in the range of 30 to 180 μm. In addition, as an optical use, the range of 30-110 micrometers is especially preferable.

[Application of optical compensation sheet]
The optical compensation sheet of the present invention can be used for an elliptically polarizing plate in combination with a polarizing film. Furthermore, by applying to a transmissive liquid crystal display device in combination with a polarizing film, it contributes to an increase in viewing angle. The elliptically polarizing plate and liquid crystal display device using the optical compensation sheet of the present invention will be described below.

[Elliptically polarizing plate]
An elliptically polarizing plate can be produced by laminating the optical compensation sheet of the present invention and a polarizing film. By using the optical compensation sheet of the present invention, an elliptically polarizing plate capable of expanding the viewing angle of the liquid crystal display device can be provided. Examples of the polarizing film include an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. The polarization axis of the polarizing film corresponds to a direction perpendicular to the stretching direction of the film.

  The polarizing film is laminated on the optically anisotropic layer side of the optical compensation sheet. It is preferable to form a transparent protective film on the surface opposite to the side on which the optical compensation sheet of the polarizing film is laminated. The transparent protective film preferably has a light transmittance of 80% or more. As the transparent protective film, generally a cellulose ester film, preferably a triacetyl cellulose film is used. The cellulose ester film is preferably formed by a solvent cast method. The thickness of the transparent protective film is preferably 20 to 500 μm, and more preferably 50 to 200 μm.

[Liquid Crystal Display]
By using the optical compensation sheet of the present invention, it is possible to provide a liquid crystal display device having a wide viewing angle. In addition, a liquid crystal display device that can display a high-quality image without display unevenness can be provided. Optical compensation sheets for TN mode liquid crystal cells are described in JP-A-6-214116, US Pat. No. 5,583,679, US Pat. No. 5,646,703, and German Patent Publication 3911620A1. Further, an optical compensation sheet for liquid crystal cells in IPS mode or FLC mode is described in JP-A-10-54982. Furthermore, OCB mode or HAN mode liquid crystal cell optical compensation sheets are described in US Pat. No. 5,805,253 and International Publication WO 96/37804. Furthermore, an optical compensation sheet for an STN mode liquid crystal cell is described in JP-A-9-26572. A VA mode liquid crystal cell optical compensation sheet is described in Japanese Patent No. 2866372.

  In the present invention, optical compensation sheets for liquid crystal cells of various modes can be produced with reference to the above publication. The optical compensation sheet of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), OCB (Optical Compensation Bend), STN (Super Tender Vend). It can be applied to a liquid crystal display device in combination with a liquid crystal cell driven in various modes such as (Hybrid Aligned Nematic) mode. The optical compensation sheet of the present invention is particularly effective in a liquid crystal display device in a TN (Twisted Nematic) mode or an OCB (Optically Compensatory Bend) mode.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, operations and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
[Example 1]
(Production of optical compensation sheet)
A triacetyl cellulose film (Fujitac, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 100 μm and a size of 270 mm × 100 mm was used as a transparent support. On the transparent support, alkyl-modified polyvinyl alcohol (MP-203, manufactured by Kuraray Co., Ltd.) was applied to a thickness of 0.5 μm and dried, and the surface was rubbed to form an alignment film. On the alignment film, a coating liquid having the following composition was applied using a bar coater.

(Optically anisotropic layer coating solution)
Fluoropolymer (P-1) 0.2 parts by mass The following discotic liquid crystalline compound (1) 100 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9.9 Mass parts photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 3.3 parts by mass Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.1 parts by mass Methyl ethyl ketone 300 parts by mass

Next, the coating layer was heated and matured at a film surface temperature of 120 ° C. for about 120 seconds, and then cooled to 80 ° C. for about 20 seconds. Subsequently, the alignment state of the optically anisotropic layer was fixed by irradiating with 0.4 J / cm ² ultraviolet rays while maintaining the same temperature. The thickness of the formed optically anisotropic layer was 1.8 μm. As described above, an optically anisotropic layer was formed to produce an optical compensation sheet.

(Evaluation of optical compensation sheet)
The unevenness of the produced optical compensation sheet was visually observed. In addition, the tilt angle in the vicinity of the alignment film of liquid crystalline molecules and the tilt angle in the vicinity of the air interface in the optically anisotropic layer of the optical compensation sheet are observed using an ellipsometer (APE-100, manufactured by Shimadzu Corporation). Retardation was measured, and the refractive index ellipsoid model was assumed, and calculated by the method described in Designing Concepts of the Discrete Birefringence Compensation Films, SID98 DIGEST. The measurement wavelength is 632.8 nm, and the results are shown in Table 1. The alignment time in the table represents the time required from the start of heat aging to the monodomain alignment of the discotic liquid crystalline compound.

[Examples 2 to 10, Comparative Examples 1 to 4]
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 fluoropolymer were changed, and unevenness evaluation and tilt angle calculation were performed in the same manner. The results are shown in Table 1.

Structure of polymer used in Comparative Example K-1: Cellulose butyrate acetate K-2: Polybutyl methacrylate (mass average molecular weight Mw = 31000)
K-3: Polyhydroxyethyl methacrylate (mass average molecular weight Mw = 22000)

  From the results shown in Table 1, in the formation of the optically anisotropic layer, the optically anisotropic layers of Examples 1 to 10 containing the fluorine-based polymer impair the rapidity of alignment in any case. It can be seen that a hybrid orientation having a high interface orientation angle can be realized without any problems. On the other hand, in Comparative Example 1 containing no fluoropolymer, although the orientation speed was high, the orientation angle at the air interface was extremely low, and sufficient hybrid orientation could not be formed. Further, in Comparative Examples 2 to 4 having optically anisotropic layers prepared using polymers (K-1 to K-3) other than fluorine-based polymers, a uniform surface shape cannot be obtained (Comparative Example 4). Even when a relatively large interfacial orientation angle could be expressed, the results showed that the orientation speed was significantly delayed (see Comparative Examples 2 and 3). From these results, the optically anisotropic layer formed from the composition containing the fluorine-based polymer forms a large interface orientation angle necessary for the performance as an optical compensation sheet, and delays the orientation speed of the liquid crystalline molecules. It turned out not to cause Furthermore, from the results of Comparative Examples 1 to 3, it was found that in the optically anisotropic layer formed from the composition containing no fluorine-based polymer, lattice-like unevenness occurred.

Next, an application example as a liquid crystal display device will be described.
[Example 11]
(Preparation of transparent support)
The following components were put into a mixing tank and heated and stirred to prepare a cellulose acetate solution (dope).
(Cellulose acetate solution composition)
Cellulose acetate having an acetylation degree of 60.9% 100 parts by mass Triphenyl phosphate 6.5 parts by mass Biphenyl diphenyl phosphate 5.2 parts by mass The following retardation increasing agent (1) 0.1 part by mass The following retardation increase Agent (2) 0.2 parts by weight Methylene chloride 310.25 parts by weight Methanol 54.75 parts by weight 1-butanol 10.95 parts by weight

  The obtained dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, both ends in the width direction of the film are fixed with a pin tenter, and the stretch rate in the width direction (direction perpendicular to the machine direction) is in a region where the solvent content is 3 to 5% by mass. Was dried while maintaining an interval of 3%. Then, it is further dried by transporting between the rolls of the heat treatment apparatus, and the stretching ratio in the machine direction is substantially 0% in the region exceeding 120 ° C. (in consideration of 4% stretching in the machine direction when stripping). A cellulose acetate film having a thickness of 100 μm was prepared by adjusting the ratio of the stretching ratio in the width direction to the stretching ratio in the machine direction to be 0.75. When the retardation of the produced film was measured at a wavelength of 632.8 nm, the retardation in the thickness direction was 40 nm, and the in-plane retardation was 4 nm. The produced cellulose acetate film was used as a transparent support.

(Formation of first undercoat layer)
On the transparent support, a coating solution having the following composition was applied at 28 ml / m ² and dried to form a first undercoat layer.

(First undercoat layer coating solution composition)
Gelatin 5.42 parts by mass Formaldehyde 1.36 parts by mass Salicylic acid 1.60 parts by mass Acetone 391 parts by mass Methanol 158 parts by mass Methylene chloride 406 parts by mass Water 12 parts by mass

(Formation of second undercoat layer)
On the first undercoat layer, a coating solution having the following composition was applied at 7 ml / m ² and dried to form a second undercoat layer.
(Second undercoat layer coating solution composition)
The following anionic polymer 0.79 parts by mass Citric acid monoethyl ester 10.1 parts by mass Acetone 200 parts by mass Methanol 877 parts by mass Water 40.5 parts by mass

(Formation of back layer)
On the opposite side of the transparent support, a coating solution having the following composition was applied at 25 ml / m ² and dried to form a back layer.
(Back layer coating solution composition)
Cellulose diacetate having an acetylation degree of 55% 6.56 parts by mass Silica matting agent (average particle size: 1 μm) 0.65 parts by mass Acetone 679 parts by mass Methanol 104 parts by mass

(Formation of alignment film)
On the second undercoat layer, an aqueous solution of alkyl-modified polyvinyl alcohol (MP-203, manufactured by Kuraray Co., Ltd.) used in Example 1 was applied, dried with warm air at 60 ° C. for 90 seconds, and then rubbed. Then, an alignment film was formed. The thickness of the obtained alignment film layer was 0.5 μm. The rubbing direction of the alignment film was parallel to the casting direction of the transparent support.

(Formation of optically anisotropic layer)
On the alignment film, a coating solution having the same composition as that of the optically anisotropic layer coating solution used in Example 1 was applied using a # 4 wire bar. The thickness of the coating layer was 1.74 μm. The film coated with the above coating solution is placed in a thermostatic bath at 130 ° C., heated to a film surface temperature of 120 ° C. over about 20 seconds, held for about 120 seconds, and then cooled to 80 ° C. for about 20 seconds. did. While maintaining the same temperature, 0.4 J / cm ² of ultraviolet light was irradiated to fix the alignment state of the liquid crystalline molecules to form an optically anisotropic layer. After cooling to room temperature, an optical compensation sheet was obtained.

(Production of liquid crystal display device)
A polyimide alignment film was formed on a glass substrate provided with an ITO transparent electrode, and a rubbing treatment was performed. The two substrates were stacked with the alignment film facing each other through a 5 μm spacer. The two substrates were arranged so that the rubbing directions of the alignment films were orthogonal. A rod-like liquid crystal molecule (ZL4792, manufactured by Merck & Co., Inc.) was injected into the gap between the substrates to form a rod-like liquid crystal layer. The birefringence Δn of the rod-like liquid crystal molecule was 0.0969. Two optical compensation sheets prepared as described above were attached to both sides of the TN liquid crystal cell manufactured as described above so that the optically anisotropic layer faces the substrate of the liquid crystal cell. Furthermore, two polarizing plates were affixed to the outside of them to produce a liquid crystal display device. The rubbing direction of the alignment film of the optical compensation sheet and the rubbing direction of the alignment film of the liquid crystal cell adjacent thereto were arranged to be antiparallel. Moreover, it arrange | positioned so that the absorption axis of a polarizing plate and the rubbing direction of a liquid crystal cell may become parallel. A voltage is applied to the liquid crystal cell of the liquid crystal display device, and the contrast ratio is 10 at the top, bottom, left, and right, respectively, with the transmittance of white display and black display in the white display 2V and the black display 5V, and there is no gradation inversion. The viewing angle was measured. The results are shown in Table 2.

(Evaluation of unevenness on LCD panel)
The display panel of the liquid crystal display device of Example 8 was adjusted to the whole halftone, and unevenness was evaluated.

[Examples 12 to 18, Comparative Example 5]
A liquid crystal display device was produced and evaluated in the same manner as in Example 11 except that the type and addition amount of the fluoropolymer were changed as shown in Table 2. The results are shown in Table 2.

  As can be seen from the results of Examples 11 to 18 and Comparative Example 5 shown in Table 2 above, an optical compensation sheet having an optically anisotropic layer formed from a composition containing a fluorine-based polymer is a field of view of a liquid crystal display device. This greatly contributes to the expansion of corners. This is presumably because the tilt angle of the liquid crystalline molecules is increased in the optically anisotropic layer in the optical compensation sheet of the example. Furthermore, as can be seen from the results of Comparative Example 5, in the liquid crystal display device having the optically anisotropic layer formed from the composition containing no fluorine-based polymer, lattice-like unevenness was observed.

Claims (8)

One or more hydrophilic groups selected from the group consisting of a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof The composition containing at least 1 type of the polymer which contains a functional group in a side chain, and a liquid crystalline compound. The composition according to claim 1, wherein the polymer is a copolymer comprising a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1).

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or a substituent; L is selected from a divalent linking group selected from the following linking group group or the following linking group group: Represents a divalent linking group formed by combining two or more,
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ — (R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ⁵ ) — (R ⁵ represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. ) The composition according to claim 1, wherein the liquid crystal compound is a discotic liquid crystal compound. The composition according to claim 3, wherein the discotic liquid crystalline compound is triphenylene liquid crystal. Furthermore, the composition of any one of Claims 1-4 containing at least 1 type of the polymer containing the repeating unit guide | induced from the fluoro aliphatic group containing monomer represented by the following general formula (A).

(In the above general formula (A), R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — (R ¹² represents a hydrogen atom or a carbon atom having 1 to 4 carbon atoms). represents an alkyl group), H ^f represents a hydrogen atom or a fluorine atom, m is 1 to 6 integer, n represents an integer of 2-4.) The polymer containing a repeating unit derived from a fluoroaliphatic group-containing monomer represented by the general formula (A) further comprises a repeating unit derived from a monomer represented by the following general formula (B). Composition.

(In the above general formula (B), R ⁶ represents a hydrogen atom or a methyl group, Z represents a divalent linking group, and R ⁷ represents a poly (alkyleneoxy) group or substituent which may have a substituent. Represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may have The optical compensation sheet which has the optically anisotropic layer formed from the composition of any one of Claims 1-6. A liquid crystal display device comprising the optical compensation sheet according to claim 7.