JP5107690B2 - Optically anisotropic film, polarizing plate, liquid crystal display device, and retardation control agent for polymer film - Google Patents

Description

  The present invention relates to a novel optical anisotropic film useful in the display field, optoelectronic field, and photonics field, and a polarizing plate and a liquid crystal display device using the same. The present invention also relates to a retardation control agent useful for producing an optically anisotropic film.

  In recent years, in the display field for displaying images, a liquid crystal display element (LCD) and a plasma display element (PDP) called a flat panel display (FPD) are widely used. In the LCD, various polymer films are used for optical compensation and the like. In order to further improve the display performance of the LCD, the optical anisotropy of these polymer films used for optical compensation (Re: retardation value in the film plane, Rth: retardation value in the film thickness direction) ) Need to be controlled and optimized. As the demand for LCD image quality increases, a method capable of freely controlling a wider area (for example, higher Re and lower Rth) has come to be required.

Patent Documents 1 and 2 disclose an optical film retardation increasing agent and the like.
Patent Document 3 includes a resin and an inorganic filler dispersed in the resin, the inorganic filler carries an organic functional agent, and a haze value at an optical path length of 1 mm of the resin composition molded body. Is a resin composition characterized in that it is 10% or less, an optical material composed of this resin composition, and an optical film formed by molding the resin composition into a film shape, as an example of an organic functional agent, Compounds having the ability to adjust retardation are mentioned. However, examples of compounds having retardation adjusting ability include only ultraviolet absorbers and infrared absorbers, and no specific structure.
European Patent Publication EP0911656A2 JP 2003-344655 A JP-A-2005-146116

An object of the present invention is to provide a novel optically anisotropic film useful in the field of display devices, and a polarizing plate and a liquid crystal display device having such an optically anisotropic film.
Another object of the present invention is to provide a novel retardation control agent for polymer films.
Another object of the present invention is to provide a technique capable of freely controlling the optical characteristics (particularly Rth) of the optical anisotropic film.

（式中、Ａ¹及びＡ²はそれぞれ、−Ｏ−、−ＮＲ−（Ｒは水素原子又は置換基を表す）、−Ｓ−及び−ＣＯ−からなる群から選ばれる基を表し；Ｚは、ベンゾ縮環又はナフト縮環を形成するのに必要な有機残基を表し；Ｒ¹はそれぞれ、置換基を表し；ｍは０〜４の整数であり、Ｒ²及びＲ³はそれぞれ、水素原子又はハメットの置換基定数σ_p値が０より大きい電子求引性の置換基を表し、Ｒ²とＲ³とが結合して環を形成してもよい。但し、Ｒ、Ｒ¹、Ｒ²又はＲ³は、オニウムカチオンを少なくとも１つ有する。） Means for solving the above problems are as follows.
[1] From the group consisting of smectite or mica and a compound represented by the following general formulas (I), (II), (III), and (IV) adsorbed to the smectite or mica by an onium cation. An optically anisotropic film comprising a molecule of at least one selected compound and a polymer material.

Wherein A ¹ and A ² each represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S— and —CO—; Represents an organic residue necessary for forming a benzo-fused ring or a naphtho-fused ring; R ¹ represents a substituent; m represents an integer of 0 to 4, and R ² and R ³ represent hydrogen, respectively. An atom or Hammett substituent constant σ _p represents an electron withdrawing substituent greater than 0, and R ² and R ³ may combine to form a ring, provided that R, R ¹ , R ² or R ³ has at least one onium cation.)

General formula (II):
Q ⁷¹ -Q ⁷² -OH
(In the general formula (II), Q ⁷¹ is a nitrogen-containing aromatic heterocyclic group, Q ⁷² represents an aromatic ring group. However, Q ⁷¹ or Q ⁷² has at least one substituent containing an onium cation. )

（一般式（III）中、Ｑ⁸¹及びＱ⁸²はそれぞれ独立に芳香族環基を表す。Ｘ⁸¹は、ＮＲ⁸¹（Ｒ⁸¹は水素原子又は置換基を表す）、酸素原子又は硫黄原子を表す。Ｑ⁸¹又はＱ⁸²は、オニウムカチオンを含む置換基を少なくとも１つ有する。）

(In the general formula (III), Q ⁸¹ and Q ⁸² each independently represents an aromatic ring group. X ⁸¹ represents NR ⁸¹ (R ⁸¹ represents a hydrogen atom or a substituent), an oxygen atom or a sulfur atom. Q ⁸¹ or Q ⁸² has at least one substituent containing an onium cation.)

（式（IV）中、Ｑ⁹¹及びＱ⁹²はそれぞれ、芳香族環基を表す。Ｘ⁹¹及びＸ⁹²はそれぞれ、水素原子又は置換基を表し、少なくともどちらか１つはシアノ基、カルボニル基、スルホニル基、芳香族ヘテロ環を表す。但し、Ｑ⁹¹、Ｑ⁹²、Ｘ⁹¹又はＸ⁹²は、置換基中にオニウムカチオンを少なくとも１つ含有する。）

(In Formula (IV), Q ⁹¹ and Q ⁹² each represent an aromatic ring group. X ⁹¹ and X ⁹² each represent a hydrogen atom or a substituent, and at least one of them represents a cyano group, a carbonyl group, A sulfonyl group and an aromatic heterocycle, provided that Q ⁹¹ , Q ⁹² , X ⁹¹ or X ⁹² contains at least one onium cation in the substituent.

[2] The optically anisotropic film according to [1], wherein the aspect ratio of the smectite or mica particles is 5 or more.
[3] The optically anisotropic film according to [1] or [2], wherein the smectite or mica is synthetic smectite or synthetic mica.
[4] The optically anisotropic film according to any one of [1] to [3], wherein the onium cation is an ammonium cation, a phosphonium cation, an imidazolium cation, or a pyridinium cation.
[5] The molecular absorption wavelength derived from the transition electric dipole moment My in the direction orthogonal to the molecular long axis direction is longer than the molecular absorption wavelength derived from the transition electric dipole moment Mx in the direction parallel to the molecular long axis direction. Further, a compound (A) having a transition electric dipole moment magnitude | My | in the direction perpendicular to the molecular long axis direction and a transition electric dipole moment in the direction parallel to the molecular long axis direction | Mx | An optically anisotropic film according to any one of [1] to [4], which is contained.
[6] An optically anisotropic film containing smectite or mica, a molecule of a compound having a mesogenic group adsorbed to the smectite or mica by an onium cation, a polymer material, and the compound (A). And
In the compound (A), the molecular absorption wavelength derived from the transition electric dipole moment My in the direction perpendicular to the molecular long axis direction is derived from the molecular absorption wavelength derived from the transition electric dipole moment Mx in the direction parallel to the molecular long axis direction. A compound having a longer wavelength and a magnitude | My | of the transition electric dipole moment in the direction perpendicular to the molecular long axis direction greater than the magnitude | Mx | of the transition electric dipole moment in the direction parallel to the molecular long axis direction. An optically anisotropic film characterized by being.

（一般式（Ｖ）中、Ｌ¹及びＬ²はそれぞれ、単結合又は二価の連結基を表す。Ｂ¹及びＢ²はそれぞれ、−Ｏ−、−ＮＲ−（Ｒは水素原子又は置換基）、−Ｓ−及び−ＣＯ−から選択される基である。Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ⁸は置換基を表す。ｎは０〜２の整数を表す。） [7] The optically anisotropic film according to [5] or [6], wherein the compound (A) is a compound represented by the following general formula (V).

(In General Formula (V), L ¹ and L ² each represent a single bond or a divalent linking group. B ¹ and B ² are each —O—, —NR— (where R is a hydrogen atom or a substituent). ), -S- and -CO-, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent substituents, and n represents an integer of 0 to 2.)

[8] The optically anisotropic film according to any one of [1] to [7], wherein the polymer material is a cellulose acylate polymer.
[9] The optically anisotropic film according to any one of [1] to [8], which is stretched.
[10] A polarizing plate having a polarizing film and a pair of protective films sandwiching the polarizing film, wherein at least one of the protective films is any one of [1] to [9] A polarizing plate characterized by being a film.
[11] A liquid crystal display device comprising the optically anisotropic film of [1] to [9] and / or the polarizing plate of [10].
[12] The liquid crystal display device according to [11], wherein the liquid crystal display device is in a VA mode.
[13] Smectite in which molecules of at least one compound selected from the group consisting of compounds represented by the general formulas (I), (II), (III), and (IV) are adsorbed by an onium cation Or the retardation control agent for polymer films which consists of mica.

In the present invention, molecules having an adsorbing group to inorganic particles are present in a polymer material in a state of being adsorbed to smectite or mica, and are expressed from the adsorption state of the molecules and the shape anisotropy of the particles. By utilizing the high orientation, it is possible to control the optical anisotropy (Rth) in the thickness direction more freely and in a wider range than the conventional technology. That is, according to the present invention, an optically anisotropic film capable of controlling Rth over a wide range can be easily produced.
Further, according to the present invention, it is possible to provide a novel optical anisotropic film useful in the field of display devices, and a polarizing plate and a liquid crystal display device having such an optical anisotropic film.
Moreover, according to this invention, the novel retardation control agent for polymer films can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, the present invention will be described in detail. In addition, in this specification, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit about a numerical range.

  The present invention relates to an optically anisotropic film containing composite particles in which molecules of a predetermined compound described later are adsorbed on smectite or mica, and a polymer material. In the present invention, a molecule of an organic compound having a predetermined structure is present in a polymer material in a state of being adsorbed to smectite or mica, and is expressed from the adsorption state of the molecule and the shape anisotropy of the particles. The optical anisotropy is controlled by utilizing high orientation. As a result, for example, compared with the conventional technique (for example, the technique disclosed in Patent Documents 1 and 2 above) in which the optical anisotropy is controlled by adding an organic compound containing an aromatic ring or the like, and more freely Optical anisotropy can be controlled over a wide range. According to the present invention, an optically anisotropic film satisfying optical characteristics required as a positive C plate or a negative C plate is obtained by selecting the shape of molecules to be adsorbed, the adsorption state of molecules, and the like. In addition, by selecting the adsorbed molecule, the wavelength dependence of the optical properties (particularly Rth) in the visible light region, the forward wavelength dispersibility (the value increases as the wavelength is shorter), and the inverse wavelength dispersibility. (The value is smaller as the wavelength is shorter) and can be arbitrarily controlled.

  In the present invention, inorganic fine particles of layered silicate, particularly smectite and mica, are used. Since smectite and mica are tabular (or layered) particles having a large aspect ratio (= particle size / thickness), when added to a polymer to form a film, these inorganic particles are highly oriented in the film. Orient horizontally in degrees. The mode of adsorption of organic molecules on tabular grains includes the "face-on adsorption" mode in which the absorption axis direction is horizontal with respect to the tabular surface of the grains, and the absorption axis direction of There is an “edge-on adsorption” mode in which adsorption is performed perpendicular to the surface. FIG. 1 (a) “face-on adsorption” and FIG. 1 (b) schematically show “edge-on adsorption”, respectively (however, regarding the relative size and shape in the figure) , It does not always reflect the actual thing). In the present invention, by adding composite particles in which molecules of a predetermined organic compound are adsorbed to tabular grains, compared to adding them in an unadsorbed state, they are present in the film with higher orientation and thickness. The direction retardation (Rth) can be set within a desired range. For example, in the “face-on” mode, Rth can be increased, and in the “edge-on” mode, Rth can be decreased. Thus, according to the present invention, by controlling the mode of adsorption, Rth can be easily increased or decreased. For example, an optical that satisfies the optical characteristics required as a positive C plate or a negative C plate. An anisotropic film can be obtained.

Usually, when a polymer film to which an organic compound is added is stretched, the molecules of the organic compound are oriented with the major axis direction aligned with the stretching direction. However, in the present invention, as shown in FIGS. 1A and 1B, the organic compound molecules in the film are present in a state of being adsorbed on tabular grains such as smectite or mica. However, it is difficult to orient in that direction. As a result, according to the present invention, it is possible to independently control only Rth without changing the in-plane retardation Re of the optically anisotropic film.
As an example, by controlling Rth by the composite particles and selecting a compound having an absorption maximum on the long wavelength side in the visible light region as a compound to be adsorbed, only a significant reverse wavelength dispersion is exhibited for Rth alone. An optically anisotropic film can be obtained.
Further, as another example, by using the composite particles as an Rth control agent and using a compound (A) satisfying predetermined conditions described later as an Re control agent, “reverse dispersibility with respect to Re, It is also possible to produce an optically anisotropic film that achieves the performance of “forward dispersion for Rth” with a single sheet. This optical performance is ideal optical performance particularly as a compensation film for a VA mode LCD.

Hereinafter, various materials used for the preparation of the optically anisotropic film of the present invention will be described.
[Smectite and mica]
There is no restriction | limiting in particular about the smectite and mica which can be used for this invention. A particle size generally in the order of nm to μm is preferred. More specifically, the average particle diameter of primary particles obtained from the diameter when the projected area is converted into a circle is preferably 5 to 500 nm, and more preferably 8 to 300 nm. Two or more kinds of fine particles having different particle size distributions and / or shapes may be mixed. In this case, the average size of the small particles is preferably 100 nm or less, more preferably 75 nm or less.
In addition, from the viewpoint of increasing the amount of organic molecules adsorbed per unit mass of the particle and expressing high orientation of the particles in the film, the shape of the smectite or mica has an aspect ratio (= particle size in the in-plane direction of the particles). (/ Particle thickness) is preferably large. The aspect ratio is preferably 5 or more, more preferably 10 or more, and still more preferably 50 or more.

  In addition to the shape anisotropy, the smectite or mica used in the present invention may further have birefringence. The difference in refractive index between the in-plane direction and the thickness direction is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.1 or more.

  The smectite or mica may be a mixture of two or more different types. When mixing and using 2 or more types of microparticles | fine-particles, each particle size and / or aspect ratio may differ.

In addition, the smectite or mica may be a natural product or a synthetic product, but a synthetic product is more preferable in that the quality is stable with few impurities. The method for preparing smectite or mica used in the present invention is not particularly limited, and the smectite or mica can be synthesized by a method according to various inorganic particles. For example, a hydrothermal synthesis method is a typical synthesis method for melting methods, intercalation methods, particularly synthetic smectites.
Commercially available products can also be used for synthetic smectite and synthetic mica. For example, Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif MAE, Somasif MTE, Somasif MEE, Somasif MPE (above manufactured by Coop Chemical Co., Ltd.), Smecton (manufactured by Kunimine Co., Ltd.) It is done.

[Organic molecules adsorbed on smectite or mica]
In the present invention, composite particles obtained by adsorbing molecules of at least one compound selected from the compounds represented by the following general formulas (I), (II), (III), and (IV) to smectite or mica are used. . The compounds represented by the following formulas (I) to (IV) each have an onium cation in one molecule, and are adsorbed on smectite or mica by the onium cation. More specifically, in the present invention, the intermolecular cation of smectite or mica is replaced by an onium cation possessed by a molecule of the compound represented by any one of the following general formulas (I) to (IV). Is adsorbed on smectite or mica.

  Hereinafter, the compound represented by formula (I) will be described.

In the formula, A ¹ and A ² each represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and —CO—. Z represents an organic residue necessary for forming a benzo condensed ring or a naphth condensed ring. R ¹ each independently represents a substituent. m is an integer of 0-4. R ² and R ³ each represents a hydrogen atom or a Hammett substituent constant σ _p value of an electron withdrawing substituent greater than 0. R, R ¹ , R ² or R ³ has at least one onium cation.

In general formula (I), A ¹ and A ² each represent a group selected from the group consisting of —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, and —CO—. Preferred is —O—, —NR— or —S—, and more preferred is —NR— or —S—.
Specific combinations of (A ¹ , A ² ) that form a heterocycle include (S, S), (S, NR), (O, NR), (NR, NR), and preferably (S, S), (S, NR), (O, NR), more preferably (S, S), (S, NR), and most preferably (S, NR).

Examples of the substituent represented by R include a substituent selected from the following substituent group.
Substituent group:
An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group ( Preferably, it is a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, a cyclopentyl group, 4-n-dodecylcyclohexyl group, a bicycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms). An unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, a bicyclo [1,2,2] heptan-2-yl group, a bicyclo [ 2,2,2] octane-3-yl group),

An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it is a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed, for example, a 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group (substituted or substituted). An unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), alkini Group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, aromatic A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably Or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy. Group),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group or tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms) Ring oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6-30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably , Substituted or non-substituted with 1 to 30 carbon atoms Carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyl An oxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group. Group), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn- Hexadecyl oxy phenoxycarbonyl group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonyl Mino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino Group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Amino groups such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylamino Sulfonylamino groups), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonyl An amino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, a mercapto group, and an alkylthio group (preferably a substituent having 1 to 30 carbon atoms) Or an unsubstituted alkylthio group such as a methylthio group Ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio A group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or An unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl and an arylsulfonyl group ( Preferably, it is substituted or substituted with 1 to 30 carbon atoms. Unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, e.g., methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p- methylphenyl sulfonyl group),

An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group or a pivaloylbenzoyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl Group (preferred Is a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- ( Methylsulfonyl) carbamoyl group),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably carbon A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinylamino group, for example, a dimethoxyphosphinylamino group, a dimethylaminophosphinylamino group, and a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, For example, trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above group or halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom) after removing this. Examples of such groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  R is preferably an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substitution having 6 to 30 carbon atoms. Or an unsubstituted aryl group or a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, more preferably an alkyl group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and more preferably an alkyl group having 1 to 15 carbon atoms and a substituted or unsubstituted cyclohexane having 3 to 15 carbon atoms. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 15 carbon atoms;

  In the general formula (I), Z forms a benzo fused ring or a naphth fused ring together with —C═C— or ═C—C═ described in the formula. However, the dotted line indicates that a double bond may be used.

In the general formula (I), R ¹ is a substituent, and when there are a plurality of R ^{1 s} , they may be the same or different and may form a ring. Examples include R or a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom).
R ¹ is preferably a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group, amino group, more preferably A halogen atom, an alkyl group, a cyano group, an alkoxy group, or an acyloxy group, and more preferably an alkoxy group or an acyloxy group. In the above substituents, it is preferred that one having an alkyl group is a chain of C ₁ -C _10. R ¹ is more preferably an alkoxy group or an acyloxy group having a C _{1 to} C ₁₀ alkyl chain.
When two or more R < ¹ > exists and forms a ring mutually, Preferably it is a 5-8 membered ring, More preferably, it is a 5 or 6 membered ring, More preferably, it is a 6 membered ring.

m represents the number of substitutions of R ¹ , and the possible number varies depending on the structure of Z, but the minimum is 0, preferably 4 or less, and more preferably 2 or less.

R ² and R ³ represents a hydrogen atom or a Hammett's substituent constant sigma _p value greater than 0 electron-withdrawing substituents, a hydrogen atom or a sigma _p value of the electron withdrawing 0-1.5 A substituent is preferable, and any of the following substituents, or a 5- or 6-membered heterocyclic group is particularly preferable.

R ⁹ and R ¹⁰ are each a hydrogen atom or a substituent, and R ⁹ and R ¹⁰ may combine to form a ring. Examples of the substituent for R are given as examples.

R ⁹ is preferably an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or 6 to 30 carbon atoms. A substituted or unsubstituted aryl group, or a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group; more preferably an alkyl group having 1 to 20 carbon atoms, 3 to 3 carbon atoms A substituted or unsubstituted cycloalkyl group having 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms; and more preferably an alkyl group having 1 to 15 carbon atoms and a substituted or unsubstituted carbon group having 3 to 15 carbon atoms. And a substituted or unsubstituted alkenyl group having 2 to 15 carbon atoms. R ¹⁰ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or 6 carbon atoms. -10 substituted or unsubstituted aryl group, or 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group; more preferably a hydrogen atom or an alkyl having 1 to 8 carbon atoms. Group, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms, and more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or A substituted or unsubstituted alkenyl group having 2 to 4 carbon atoms.
Regarding σ _p of Hammett's substituent constant, for example, Naoki Inamoto, “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan, “New Experimental Chemistry Course 14 Synthesis and Reaction V of Organic Compounds” 2605 (Maruzen), Tadao Nakatani, “Explanation on Theoretical Organic Chemistry”, page 217 (Tokyo Kagaku Dojin), Chemical Review, Vol. 91, pages 165-195 (1991).

In the general formula (I), R, R ¹ , R ² or R ³ contains at least one onium cation. Examples of the onium cation will be described later.

Next, the compound represented by formula (II) will be described.
Formula ^{(II): Q 71 -Q 72} -OH
Wherein, Q ⁷¹ is a nitrogen-containing aromatic heterocyclic group, Q ⁷² represents an aromatic ring group. Q ⁷¹ or Q ⁷² has at least one substituent containing an onium cation.

In the general formula (II), Q ⁷¹ represents a nitrogen-containing aromatic heterocyclic group, preferably a 5- to 7-membered nitrogen-containing aromatic heterocyclic group, more preferably a 5- to 6-membered nitrogen-containing aromatic group. It is a heterocyclic group.
Preferred examples of the nitrogen-containing aromatic heterocyclic ring Q ⁷¹ has, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzotriazole, benzothiazole, benzoxazole, benzoselenazole, thiadiazole, oxadiazole, naphtho Each ring includes thiazole, naphthoxazole, azabenzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, triazaindene, tetrazaindene, etc., more preferably triazine and 5-membered nitrogen-containing aromatic Heterocycle, specifically 1,3,5-triazine, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, benzotriazole, benzothiazole, benzox Tetrazole, thiadiazole, each ring such as oxadiazole Preferably, particularly preferably a 1,3,5-triazine ring and a benzotriazole ring.

Nitrogen-containing aromatic heterocyclic group represented by Q ⁷¹ may further have a substituent group, the substituent is preferably selected from Substituent Group T described later. In addition, when there are a plurality of substituents, each may be condensed to form a ring.

Q ⁷² represents an aromatic ring group. Aromatic ring Q ⁷² has may be an aromatic hetero ring in the aromatic hydrocarbon ring. These may be monocyclic or may form a condensed ring with another ring.
The aromatic hydrocarbon ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (such as a benzene ring or a naphthalene ring), more preferably 6 to 20 carbon atoms. An aromatic hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms. More preferred is a benzene ring.
The aromatic heterocycle is preferably an aromatic heterocycle containing a nitrogen atom or a sulfur atom. Specific examples of the heterocyclic ring include, for example, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, Examples include phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, and tetrazaindene. Preferred examples of the aromatic heterocycle include pyridine, triazine, and quinoline.

The aromatic ring represented by Q ^72, is preferably an aromatic hydrocarbon ring, more preferably a naphthalene ring, a benzene ring, particularly preferably a benzene ring. Q ⁷² may further have a substituent, and the substituent is preferably selected from the following substituent group T.

Substituent group T:
An alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n -Decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably having 2-20 carbon atoms, more preferably 2-12 carbon atoms, particularly preferably 2-8 carbon atoms such as vinyl Group, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2-20 carbon atoms, more preferably 2-12, particularly preferably 2-8, such as propargyl group, 3- A pentynyl group), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms such as a phenyl group. A biphenyl group, a naphthyl group, etc.), an amino group (preferably having a carbon number of 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, A dibenzylamino group), an alkoxy group (preferably having a carbon number of 1-20, more preferably 1-12, particularly preferably 1-8, such as a methoxy group, an ethoxy group, a butoxy group, etc.), an aryloxy group ( Preferably it has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy group, 2-naphthyloxy group, etc., acyl group (preferably 1 to 20 carbon atoms, more preferably Are 1 to 16, particularly preferably 1 to 12, such as acetyl, benzoyl, formyl, and pivaloyl) Sicarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group), aryloxycarbonyl group (preferably having 7 to 7 carbon atoms) 20, more preferably 7 to 16, particularly preferably 7 to 10, for example, phenyloxycarbonyl group, etc., acyloxy group (preferably 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, a benzoyloxy group),

An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms) , More preferably 2 to 16, particularly preferably 2 to 12, for example, methoxycarbonylamino group and the like, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 carbon atoms). -12, for example, phenyloxycarbonylamino group, etc., sulfonylamino group (preferably 1-20 carbon atoms, more preferably 1-16, particularly preferably 1-12, such as methanesulfonylamino group, benzenesulfonyl Amino groups, etc.), sulfamoyl groups (preferably having 0 to 20 carbon atoms, More preferably, it is 0-16, Most preferably, it is 0-12, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms). More preferably 1 to 16, particularly preferably 1 to 12, for example, a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group, etc., an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1). -16, particularly preferably 1-12, for example, methylthio group, ethylthio group, etc.), arylthio group (preferably 6-20, more preferably 6-16, particularly preferably 6-12, such as phenylthio Group), a sulfonyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include a mesyl group and a tosyl group.), A sulfinyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 16, and particularly preferably 1 to 12). For example, methanesulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as ureido group, methylureido group, phenyl Ureido group), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, such as diethyl phosphoric acid amide and phenylphosphoric acid amide),

Hydroxy group, mercapto group, halogen atom (eg 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, hetero A cyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, an imidazolyl group, a pyridyl group, a quinolyl group, Furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like, and silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms). For example, trimethylsilyl group, triphenylsilyl group, etc.).

  These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

Q ⁷¹ or Q ⁷² has at least one substituent containing an onium cation. The onium cation will be described later.

  Next, the compound represented by formula (III) will be described.

In the general formula (III), Q ⁸¹ and Q ⁸² each independently represents an aromatic ring group. X ⁸¹ represents NR ⁸¹ (R ⁸¹ represents a hydrogen atom or a substituent), an oxygen atom or a sulfur atom. Q ⁸¹ or Q ⁸² has at least one substituent containing an onium cation.

The aromatic ring group represented by Q ⁸¹ and Q ⁸² may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The aromatic hydrocarbon ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring or a naphthalene ring), and more preferably an aromatic hydrocarbon having 6 to 20 carbon atoms. It is a hydrocarbon ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and particularly preferably a benzene ring.
The aromatic heterocycle is preferably an aromatic heterocycle containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of the aromatic heterocycle include furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, Each ring includes quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzotriazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocycle, a pyridine ring, a triazine ring, or a quinoline ring is preferable.

The aromatic ring group represented by Q ⁸¹ and Q ⁸² is preferably an aromatic hydrocarbon ring group, more preferably an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, substituted or unsubstituted. The benzene ring group (phenyl group or phenylene group) is more preferable.

Q ⁸¹ and Q ⁸² may have a substituent, and the substituent is preferably a substituent selected from the substituent group T described above. When possible, substituents may be linked to form a ring structure. Q ⁸¹ or Q ⁸² has at least one substituent containing an onium cation. The onium cation will be described later.

X ⁸¹ represents NR ⁸¹ (R ⁸¹ represents a hydrogen atom or a substituent, and the substituent is preferably a substituent selected from the above substituent group T), an oxygen atom or a sulfur atom. X ⁸¹ is preferably NR ⁸¹ (R ⁸¹ is preferably an acyl group or a sulfonyl group, and these substituents may be further substituted) or an oxygen atom, and particularly preferably an oxygen atom.

The compound represented by general formula (IV) is demonstrated below.

In the general formula (IV), Q ⁹¹ and Q ⁹² each represents an aromatic ring group. X ⁹¹ and X ⁹² each represent a hydrogen atom or a substituent, and at least one of them represents a cyano group, a carbonyl group, a sulfonyl group, or an aromatic heterocycle. At least one onium cation is contained in the substituent of Q ⁹¹ , Q ⁹² , X ⁹¹ or X ⁹² .

In the general formula (IV), Q ⁹¹ and Q ⁹² each represents an aromatic ring group. The aromatic ring group represented by Q ⁹¹ and Q ⁹² may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. These may be monocyclic or may form a condensed ring with another ring. Furthermore, you may form a condensed ring with another ring.

The aromatic hydrocarbon ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring or a naphthalene ring), and more preferably an aromatic carbon ring having 6 to 20 carbon atoms. A hydrogen ring, more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms, and particularly preferably a benzene ring.
The aromatic heterocycle is preferably an aromatic heterocycle containing a nitrogen atom or a sulfur atom. Specific examples of the heterocyclic ring include thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, Examples include naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. Preferred examples of the aromatic heterocycle include pyridine, triazine, and quinoline.

Q ⁹¹ and Q ⁹² are each preferably an aromatic hydrocarbon ring group, and more preferably a phenyl group.
Q ⁹¹ and Q ⁹² may further have a substituent, and the substituent is preferably selected from the substituent group T.

X ⁹¹ and X ⁹² each represent a hydrogen atom or a substituent, and at least one of them represents a cyano group, a carbonyl group, a sulfonyl group, or an aromatic heterocycle. The substituents represented by X ⁹¹ and X ⁹² are preferably selected from the substituent group T. The substituents represented by X ⁹¹ and X ⁹² may be further substituted with other substituents, and X ⁹¹ and X ⁹² may each be condensed to form a ring structure.

X ⁹¹ and X ⁹² are preferably a hydrogen atom, an alkyl group, an aryl group, a cyano group, a nitro group, a carbonyl group, a sulfonyl group, or an aromatic heterocyclic group, more preferably a cyano group, a carbonyl group, A sulfonyl group or an aromatic heterocyclic group, more preferably a cyano group or a carbonyl group, and particularly preferably a cyano group or an alkoxycarbonyl group {—C (═O) OR ⁹¹ (R ⁹¹ is the number of carbon atoms) 1-20 alkyl groups, C6-C12 aryl groups, and combinations thereof)}.

At least one onium cation is contained in the substituent of Q ⁹¹ , Q ⁹² , X ⁹¹ or X ⁹² . The onium cation will be described later.

  Preferable examples of the compound represented by the general formula (IV) include a compound represented by the following general formula (IV-I).

In the formula, R ⁹¹¹ , R ⁹¹² , R ⁹¹³ , R ⁹¹⁴ , R ⁹¹⁵ , R ⁹¹⁶ , R ⁹¹⁷ , R ⁹¹⁸ and R ⁹¹⁹ each independently represent a hydrogen atom or a substituent, It is preferably selected from the group T. Further, these substituents may be further substituted with another substituent, and the substituents may be condensed to form a ring structure. X ⁹¹¹ and X ⁹¹² are synonymous with X ⁹¹ and X ⁹² in the general formula (IV), respectively.

R ⁹¹¹ , R ⁹¹² , R ⁹¹⁴ , R ⁹¹⁵ , R ⁹¹⁶ , R ⁹¹⁷ and R ⁹¹⁹ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, An aryloxy group, a hydroxy group, or a halogen atom; more preferably a hydrogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, or a halogen atom; still more preferably a hydrogen atom, or carbon 1-12. An alkyl group; particularly preferably a hydrogen atom or a methyl group; and most preferably a hydrogen atom.

R ⁹¹³ and R ⁹¹⁸ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a hydroxy group, or a halogen atom; Preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or a hydroxy group; A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms; particularly preferably a hydrogen atom.

R ⁹¹¹ , R ⁹¹² , R ⁹¹³ , R ⁹¹⁴ , R ⁹¹⁵ , R ⁹¹⁶ , R ⁹¹⁷ , R ⁹¹⁸ , R ⁹¹⁹ , X ⁹¹¹ or X ⁹¹² have at least one onium cation. The onium cation will be described later.

  Any molecule of the compounds represented by the general formulas (I) to (IV) has an onium cation in one molecule, and is adsorbed to smectite or mica by the onium cation. As described above, more specifically, by replacing the onium cation in the molecule of the compound represented by the general formulas (I) to (IV) with an exchangeable cation that mica or smectite particles have between layers. The molecule is adsorbed on mica or smectite.

As an onium cation, an ammonium cation, a phosphonium cation, and a heterocyclic onium cation are preferable. Examples of ammonium cations include aliphatic quaternary ammonium ions and alicyclic quaternary ammonium ions. Examples of the phosphonium cation include aliphatic phosphonium ions and aromatic phosphonium ions.
As the heterocyclic onium cation, an imidazolium cation or a pyridinium cation is preferable.

  A linking group may exist between the onium cation and a group having a ring structure such as an aromatic ring group in the compounds represented by formulas (I) to (IV). Examples of the linking group include substituted or unsubstituted linear or branched alkylene having 1 to 18 (preferably 1 to 6) carbon atoms; substituted or unsubstituted ether having 1 to 18 (preferably 1 to 6) carbon atoms. Linear or branched alkylene having an intervening bond; substituted or unsubstituted arylene having 6 to 18 carbon atoms (preferably 6 to 12); -O-, -NH-, -S-, -CONH-, -NHCO-, And a 5- or 6-membered heterocyclic group.

  The organic molecule adsorbed on the smectite or mica preferably has a long-chain alkyl group having 8 to 30 carbon atoms in order to improve the dispersibility of the layered or tabular smectite or mica in the solvent / polymer. The alkyl group may be linear, branched, or have a cyclic structure, but more preferably has a branch.

The organic molecule adsorbed on smectite or mica preferably further has a substituent having an affinity for the polymer material used in combination. The affinity between the substituent and the polymer material can be estimated by referring to the respective solubility parameters (SP values) of the polymer material and the substituent, and the sp values are preferably close to each other. Here, the calculation of sp value can refer to the method by Hoy et al. Described in Journal of Paint Technology, 42, 76, 1970. The SP value of the polymer material is expressed by the following formula: SP = a ₁ × SP ₁ + a ₂ × SP ₂ + a ₃ × SP ₃ +.
Can be obtained by calculation. Here, SP ₁ , SP ₂ and SP ₃ in the formula represent the SP values of the respective homopolymers obtained when the monomers contained in the monomer components of the respective polymers are individually polymerized, and “POLYMER” This is a value obtained by quoting the value described in “HANDBOOK THIRD EDITION”. Further, a ₁ , a ₂ and a ₃ in the above formulas represent mass fractions of the monomers contained in the monomer component used to form each polymer.

  A preferable example of the substituent varies depending on the polymer material used. In many cases, a linear or branched alkyl group often functions effectively. For example, when an acrylic polymer such as PMMA is used as a polymer material, the adsorbing organic molecule includes a CO group and a COO group. Those having a substituent are preferred; when a cellulose acylate polymer is used as the polymer material, the adsorbed organic molecule has an ether group as a substituent (preferably an alkoxyalkyloxy group, particularly preferably 3- Methoxybutoxy), those having a carbonyl group as a substituent, and those having a sugar derivative as a substituent are preferred.

  Although the specific example of the organic compound represented by the said general formula (I) used for this invention below is shown, it is not limited to these.

  Although the specific example of the organic compound represented by the said general formula (II) used for this invention below is shown, it is not limited to these.

  Although the specific example of the organic compound represented by the said general formula (III) used for this invention below is shown, it is not limited to these.

  Although the specific example of the organic compound represented by the said general formula (IV) used for this invention below is shown, it is not limited to these.

The compounds represented by the formulas (I) to (IV) are preferably compounds having an absorption maximum on the long wavelength side of the UV wavelength region (specifically, in the range of about 250 to 380 nm). It is preferable to use composite particles in which a compound having an absorption maximum in this range is “face-on adsorbed” because Rth of the optically anisotropic film can be made forwardly dispersible.

[Organic molecule having mesogenic group adsorbed on smectite or mica]
Instead of adsorbing any molecule of the compounds represented by the general formulas (I) to (IV) to smectite or mica, composite particles in which molecules of a compound having a mesogenic group are adsorbed by an onium cation are used. The same effect can be obtained by using it. However, when using the composite particles of this embodiment, it is preferable to use a compound (A) that satisfies the conditions described later.

“Mesogenic group” refers to a group that can form the core of a liquid crystal compound, and examples of the compound having a mesogenic group include a liquid crystalline compound and a mesogenic group, but does not form a liquid crystal. Non-liquid crystalline compounds are also included.
The mesogenic group will be further described. In the present invention, the mesogenic group is a group showing a main skeleton of liquid crystal molecules that contribute to liquid crystal formation. The liquid crystal molecules exhibit liquid crystallinity that is an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. The mesogenic group is not particularly limited. For example, “Flushage Kristall in Tablen II” (VEB Deutsche Verlag fur Grundoff Industrie, Leipzig, published in 1984), pages 7 to 16 You can refer to the editions of the association, Liquid Crystal Handbook (Maruzen, 2000), especially the description in Chapter 3. A residue of a thermotropic liquid crystal is preferable, and a residue of a rod-like liquid crystal and a discotic liquid crystal is more preferable. In the rod-like liquid crystal, a liquid crystal residue showing a nematic phase and a smectic A phase is more preferable, and in a discotic liquid crystal, a liquid crystal residue showing a discotic nematic phase is more preferable.

  Preferred examples of the residue of the discotic liquid crystal include benzene, triphenylene, truxene, trioxatruxene, anthraquinone, phthalocyanine or porphyrin, macrocyclene, bis (1,3-diketone) copper complex, tetraarylbipyranylidene, Tetrathiafulvalene and inositol are included.

  Examples of the main skeleton of the liquid crystal molecules that contribute to the formation of a rigid liquid crystal called a mesogenic group or a core portion of the rod-like liquid crystal, that is, the residue of the rod-like liquid crystal include groups represented by the following general formula (VI).

上記一般式（VI）中、Ｌ³及びＬ⁴は単結合又は二価の連結基を表す。二価の連結基としては−Ｏ−、−Ｓ−、−ＣＯ−、−ＮＲ⁰−（Ｒ⁰は水素原子（Ｈ）、メチル基及びエチル基より選ばれる置換基を表す）、−ＣＨ＝Ｎ−、−Ｎ＝Ｎ−、二価の鎖状基、二価の環状基及びそれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。
二価の鎖状基としては、アルキレン基、アルケニレン基又はアルキニレン基が好ましい。これらは分岐又は置換基を有していてもよい。より好ましい炭素数としては２〜８であり、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、２−メチル−テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、２−ブテニレン基、２−ブチニレン基が好適な例として挙げられる。二価の環状基としては、後述するＣｙ¹〜Ｃｙ³が好ましい。

In the general formula (VI), L ³ and L ⁴ represent a single bond or a divalent linking group. As the divalent linking group, —O—, —S—, —CO—, —NR ⁰ — (R ⁰ represents a substituent selected from a hydrogen atom (H), a methyl group and an ethyl group), —CH═ A divalent linking group selected from the group consisting of N-, -N = N-, a divalent chain group, a divalent cyclic group, and combinations thereof is preferable.
As the divalent chain group, an alkylene group, an alkenylene group or an alkynylene group is preferable. These may have a branched or substituted group. More preferable carbon number is 2-8, ethylene group, trimethylene group, propylene group, tetramethylene group, 2-methyl-tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, 2-butenylene group, A 2-butynylene group is a suitable example. As the divalent cyclic group, Cy ¹ to Cy ³ described later are preferable.

In the general formula (VI), Cy ¹ , Cy ² and Cy ³ each independently represent a divalent cyclic group. It is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. A single ring or a condensed ring may be used, and a single ring is preferable. Any of an aromatic ring, an aliphatic ring, and a heterocyclic ring may be sufficient. Among these, preferred examples of the aromatic ring include a benzene ring (particularly 1,4-phenylene group) and a naphthalene ring (particularly naphthalene-1,5-diyl group and naphthalene-2,6-diyl group). Preferred examples of the aliphatic ring include a cyclohexane ring (particularly 1,4-cyclohexylene group) and a bicyclo [2.2.2] octane ring, and examples of the heterocyclic ring include a pyridine ring (particularly pyridine-2, Preferred examples include 5-diyl group), pyrimidine ring (particularly pyrimidine-2,5-diyl group), thiophene ring (particularly thiophene-2,5-diyl group) and dioxane ring. Cy ¹ , Cy ² and Cy ³ may each independently have a substituent. Examples of preferable substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom, and 1 to 5 carbon atoms. Substituted with an alkoxy group, an alkylthio group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, or an alkyl group having 2 to 6 carbon atoms Examples thereof include a carbamoyl group and an acylamino group having 2 to 6 carbon atoms.

In said general formula (VI), p represents the integer of 0-2. When p is 2, the two L ⁴ and Cy ² may be the same or different.

  Preferred examples of the residue (mesogen group) of the rod-like liquid crystal include a biphenyl group, a phenylenecarbonyloxybiphenyl group, a carbonyloxybiphenyl group, a terphenyl group, a naphthylenecarbonyloxyphenyl group, a phenyleneethenylenecarbonyloxybiphenyl group, and a phenyleneethene. Nylene phenyl group, benzoic acid phenyl ester group, benzylidene aniline group, azobenzene group, azoxybenzene group, stilbene group, phenyleneethynylenecarbonyloxybiphenyl group, naphthylene biphenyl group, and those whose benzene ring is saturated or Includes substitutions for heterocycles.

In the present invention, a compound having an onium cation group that is an adsorbing group to smectite or mica is used together with a mesogenic group.
Specific examples of compounds having an onium cation as an adsorbing group to inorganic particles and having a mesogenic group capable of forming the core of a liquid crystal compound are shown below, but are not limited thereto. .

The smectite or mica on which a predetermined compound is adsorbed can be obtained by mixing smectite or mica and the compound, bringing them into contact with each other, and consequently physically adsorbing and / or chemisorbing the compound on the smectite or mica. In mixing and contacting, a solvent can be used, and it can be carried out in the state of a polymer dope described later. Whether smectite or mica adsorbs the compound can be confirmed by measuring an ultraviolet-visible absorption spectrum, an infrared absorption spectrum, and a thermal analysis. The adsorption of the compound on smectite or mica is preferably a single layer coating. Since the surface area per unit mass varies depending on the particle size, the preferred amount varies depending on the particle size, but it is preferably 10 to 300% by mass, more preferably 20 to 150% by mass. preferable.
In addition, when the composition containing the composite particles and the polymer material is prepared as a dope or a coating solution, and used for the production of an optically anisotropic film, the compound is adsorbed on smectite or mica in the dope and the coating solution. For example, adsorption of the compound to smectite or mica may proceed in the process of casting a dope or applying a coating solution and then drying.

  In addition, when adsorbing the compound to smectite or mica, it is possible to control adsorption on the smectite or mica at the end or by adsorbing on the surface by introducing an adsorption group at a specific position of the molecule. it can. In addition, it is possible to adsorb molecules to specific parts of the inorganic particles by combining the adsorption group species and the characteristics of the particle surface.

  The amount of the composite particles added is generally preferably 0.5 to 20% by mass, and preferably 1 to 10% by mass, based on the total mass of the composition used for producing the optically anisotropic film. Is more preferable.

[Polymer material]
In the present invention, the term “polymer material” is used in the meaning including both natural polymers and synthetic polymers. When producing the optically anisotropic film of the present invention, it is preferable to use a polymer material that can be formed into a film. Examples of polymer materials that can be formed into a film include cellulose derivatives, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, polyethylene terephthalate, polyethylene naphthalate, syndiotactic polyester, polyphenylene sulfide. , Polyarylate, polyester sulfone, polyimide, polyetherimide, cyclic polyolefin resin, brominated phenoxy resin, and the like. Of these, cyclic polyolefin resins called COC and COP, and cellulose derivatives are preferable. Particularly preferred is cellulose acylate.
Hereinafter, cellulose acylate will be described in detail.

[Cellulose acylate]
As the raw material cotton of cellulose acylate, a known raw material can be used (for example, refer to Japanese Society of Invention and Innovation technique 2001-1745). Cellulose acylate can also be synthesized by a known method (for example, see Mita et al., Wood Chemistry pages 180-190 (Kyoritsu Shuppan, 1968)). The viscosity average degree of polymerization of the cellulose acylate is preferably 200 to 700, more preferably 250 to 500, and most preferably 250 to 350. Further, the number average molecular weight (Mn) of the cellulose acylate used in the present invention is preferably 10,000 to 150,000, the weight average molecular weight (Mw) is 20,000 to 500,000, and the Z average molecular weight (Mz) is preferably 5,000 to 550000. Moreover, it is preferable that the molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography is narrow. The specific value of Mw / Mn is preferably 1.5 to 5.0, more preferably 2.0 to 4.5, and most preferably 3.0 to 4.0. preferable.

The acyl group of the cellulose acylate is not particularly limited, but an acetyl group, propionyl group, butyryl group or benzoyl group is preferably used. The substitution degree of all acyl groups is preferably 2.0 to 3.0, more preferably 2.2 to 2.95. In this specification, the substitution degree of an acyl group is a value calculated according to ASTM D817. The acyl group is most preferably an acetyl group, and in the case of using cellulose acetate in which the acyl group is an acetyl group, the acetylation degree is preferably 57.0 to 62.5%, and 58.0 More preferably, it is 62.0%. When the acetylation degree is within this range, Re does not become larger than the desired value due to the conveying tension during casting, there is little in-plane variation, and there is little change in the retardation value due to temperature and humidity.
In particular, it is obtained by substituting the hydroxyl group of the glucose unit constituting the cellulose of the cellulose acylate with an acyl group having 2 or more carbon atoms. When the degree of substitution of the hydroxyl group with an acyl group is DS3 and the degree of substitution of the hydroxyl group at the 6-position with DS6 is DS6, if the following formulas (1) and (2) are satisfied, desired Re and Rth can be easily obtained. In addition, the Re value variation due to temperature and humidity becomes smaller, which is preferable.
(1): 2.0 ≦ (DS2 + DS3 + DS6) ≦ 3.0
(2): DS6 / (DS2 + DS3 + DS6) ≧ 0.315
A more preferred range is
(1 ′): 2.2 ≦ (DS2 + DS3 + DS6) ≦ 2.9
(2 ′): DS6 / (DS2 + DS3 + DS6) ≧ 0.322.

Or in particular, when the substitution degree of the hydroxyl group of the glucose unit of cellulose acylate by A and the substitution degree by propionyl group or butyryl group or benzoyl group is B, A and B are represented by formulas (3) and (4). When it is satisfied, it becomes easy to obtain desired Re and Rth, and it is easy to realize a high draw ratio without breaking, which is preferable.
(3): 2.0 ≦ A + B ≦ 3.0
(4): 0 <B
A more preferred range is
(3 ′): 2.6 ≦ A + B ≦ 3.0
(4 ′): 0.5 ≦ B ≦ 1.5
It is.

[Polymers other than cellulose acylate]
The polymer material used in the present invention is not limited to cellulose acylate, and for example, a polycarbonate copolymer or a polymer resin having a cyclic olefin structure can be used.
Examples of the polycarbonate copolymer include a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B), and the repeating unit represented by the above formula (A) is 80 to 30 mol in total. % Of the polycarbonate copolymer.

In the above formula (A), R ^{1 to} R ⁸ are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as a methyl group, an ethyl group, an isopropyl group, and a cyclohexyl group, and an aryl group such as a phenyl group. Among these, a hydrogen atom and a methyl group are preferable.

X is the following formula (X), and R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include the same ones as described above.

In the above formula (B), R ^{11 to} R ¹⁸ are each independently selected from a hydrogen atom, a halon atom, and a hydrocarbon group having 1 to 22 carbon atoms. Examples of the hydrocarbon group having 1 to 22 carbon atoms include alkyl groups having 1 to 9 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a cyclohexyl group, and aryl groups such as a phenyl group, a biphenyl group, and a terphenyl group. It is done. Among these, a hydrogen atom and a methyl group are preferable.

Y is the following group of formulas, and R ^{19 to} R ²¹ , R ²³ and R ²⁴ are each independently at least one group selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 22 carbon atoms. Examples of the hydrocarbon group include the same ones as described above. R ²² and R ²⁵ are each independently selected from hydrocarbon groups having 1 to 20 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a cyclohexylene group, a phenylene group, a naphthylene group, A terphenylene group is mentioned. Examples of Ar ^{1 to} Ar ³ include aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.

  As said polycarbonate copolymer, the polycarbonate copolymer which consists of 30-60 mol% of repeating units shown by the following formula (C), and 70-40 mol% of repeating units shown by the following formula (D) is preferable.

  More preferably, it is a polycarbonate copolymer composed of 45 to 55 mol% of the repeating unit represented by the above formula (C) and 55 to 45 mol% of the repeating unit represented by the above formula (D).

In the formula (C), R ^{26 to} R ²⁷ are each independently a hydrogen atom or a methyl group, and preferably a methyl group from the viewpoint of handleability.

In the above formula (D), R ^{28 to} R ²⁹ are each independently a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of economy, film characteristics, and the like.

  The optically anisotropic film of the present invention preferably uses the above-described polycarbonate copolymer having a fluorene skeleton. As the polycarbonate copolymer having a fluorene skeleton, for example, a blend of polycarbonate copolymers having different composition ratios composed of the repeating unit represented by the above formula (A) and the repeating unit represented by the above formula (B) is often used. The content of the above formula (A) is preferably 80 to 30 mol%, more preferably 75 to 35 mol%, still more preferably 70 to 40 mol% of the entire polycarbonate copolymer.

  The copolymer may be a combination of two or more repeating units represented by the above formulas (A) and (B).

  Here, the molar ratio is a molar ratio with respect to the entire polycarbonate bulk constituting the optical film, and can be determined by, for example, a nuclear magnetic resonance (NMR) apparatus.

  The above polycarbonate copolymer can be produced by a known method. As the polycarbonate, a method by polycondensation of a dihydroxy compound and phosgene, a melt polycondensation method or the like is preferably used.

  The intrinsic viscosity of the polycarbonate copolymer is preferably 0.3 to 2.0 dl / g. If it is less than 0.3, there is a problem that it becomes brittle and the mechanical strength cannot be maintained. There is a problem of becoming.

The optically anisotropic film of the present invention may be formed from a composition (blend) of the polycarbonate copolymer and other polymer compound. In this case, since the polymer compound needs to be optically transparent, it is preferable that the polymer compound is compatible with the polycarbonate copolymer, or the refractive index of each polymer is substantially equal. Specific examples of the other polymer include styrene-maleic anhydride copolymer, and the composition ratio of the polycarbonate copolymer to the polymer compound is 80 to 30% by mass of the polycarbonate copolymer. They are 20-70 mass%, Preferably they are a polycarbonate copolymer 80-40 mass%, and a high molecular compound body 20-60 mass%. Also in the case of a blend, two or more kinds of repeating units of the polycarbonate copolymer may be combined. In the case of a blend, a compatible blend is preferable. However, even if the blend is not completely compatible, the light scattering between the components can be suppressed and the transparency can be improved by adjusting the refractive index between the components. In addition, a blend body may combine 3 or more types of materials, and can combine multiple types of polycarbonate copolymer and another high molecular compound.
The weight average molecular weight of the polycarbonate copolymer is 1,000 to 1,000,000, preferably 5,000 to 500,000. The mass average molecular weight of the other polymer compound is 500 to 100,000, preferably 1,000 to 50,000.

  Examples of the polymer material other than cellulose acylate include a polymer resin having a cyclic olefin structure (hereinafter also referred to as “cyclic polyolefin resin” or “cyclic polyolefin”). Examples include (1) norbornene polymers, (2) monocyclic olefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, and (1 ) To (4) hydrides. Preferred polymers for the present invention are addition (co) polymer cyclic polyolefins containing at least one repeating unit represented by the following general formula (XI), and, if necessary, a repeating unit represented by the general formula (I) An addition (co) polymer cyclic polyolefin further comprising at least one of the above. Further, addition (co) polymers (including ring-opening (co) polymers) containing at least one cyclic repeating unit represented by the general formula (XII) can also be suitably used. The addition (co) polymer cyclic further comprising at least one repeating unit represented by the general formula (XII) and, if necessary, at least one repeating unit represented by the general formula (X). Polyolefins can also be preferably used.

In formula, m represents the integer of 0-4. R ^{11 to} R ¹⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X ^{1 to} X ³ and Y ^{1 to} Y ³ are each a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen _{atom, - (CH 2) n COOR} 21, - (CH 2) n OCOR 22, - (CH 2) n NCO, - (CH 2) _{n NO 2, - (CH 2} ) n CN, - (CH 2) n CONR 23 R 24, - (CH 2) n NR 23 R 24, - (CH 2) n OZ, - (CH 2) n W, Or (—CO) ₂ O, (—CO) ₂ NR ²⁵ composed of X ¹ and Y ¹ , X ² and Y ^2, or X ³ and Y ³ . R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; Z is a hydrocarbon group or a hydrocarbon group substituted with a halogen; SiR ²⁶ _p D _3-p (R ²⁶ is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom —OCOR ²⁶ or OR ²⁶ , p is an integer of 0 to 3); n is an integer of 0 to 10 Indicates.

By introducing a polarizable large functional group in a substituent ^{X 1 ~X 3, Y 1 ~Y} 3, by increasing the thickness-direction retardation of the optically anisotropic film (Rth), in-plane retardation ( The expression of Re) can be increased. An optically anisotropic film having a large Re developing property can have a large Re value by stretching in the film forming process.
Norbornene type addition (co) polymers are disclosed in JP-A-10-7732, JP-T-2002-504184, US2004229157A1 or WO2004 / 070463A1. It can be obtained by addition polymerization of norbornene-based polycyclic unsaturated compounds. If necessary, norbornene-based polycyclic unsaturated compounds and conjugated dienes such as ethylene, propylene, butene, butadiene and isoprene; non-conjugated dienes such as ethylidene norbornene; acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride It is also possible to carry out addition polymerization with linear diene compounds such as acid, acrylic acid ester, methacrylic acid ester, maleimide, vinyl acetate and vinyl chloride. This norbornene-based addition (co) polymer is marketed by Mitsui Chemicals, Inc. under the name of Apel, and has different glass transition temperatures (Tg) such as APL8008T (Tg70 ° C), APL6013T (Tg125 ° C) or APL6015T ( Grades such as Tg145 ° C). Pellets are sold under the trade names such as TOPAS 8007, 6013, and 6015 from Polyplastics. Further, Appear 3000 is sold by Ferrania.

Norbornene polymer hydrides are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, JP-A-2003-159767, JP-A-2004-309799. As disclosed in various publications such as No. 1, etc., it is prepared by addition polymerization or metathesis ring-opening polymerization of a polycyclic unsaturated compound and then hydrogenation. In the norbornene-based polymer used in the present invention, R ^{5 to} R ⁶ are preferably a hydrogen atom or —CH ₃ , X ³ and Y ³ are preferably a hydrogen atom, Cl, —COOCH ₃ , and other groups are appropriately selected. . This norbornene-based resin is sold under the trade name Arton G or Arton F by JSR Corporation, and from Zeon Corporation, Zeonor ZF14, ZF16, Zeonex 250 or Zeonex. They are commercially available under the trade name 280 and can be used.

The optically anisotropic film of the present invention may contain other additives in addition to the composite particles and the polymer material as long as the effects of the present invention are not impaired. It is also possible to include a compound having a photosensitive isomerization group. About these, Polymer, 41 (12), (1992) p884, "Chromic materials and applications" (published by CMC) p221, "Mechanochemistry" (Maruzen published) p21, "Polymer papers 147, 10" (1991) p771 and the like.
Hereinafter, examples of additives that can be added to the optically isotropic film of the present invention will be described.

[Re (in-plane retardation) developing agent]
The optically anisotropic film of the present invention preferably contains a compound (A) satisfying the following conditions as a Re (in-plane retardation) developing agent together with the composite particles described above.
Compound (A): The molecular absorption wavelength derived from the transition electric dipole moment My in the direction orthogonal to the molecular long axis direction is longer than the molecular absorption wavelength derived from the transition electric dipole moment Mx in the direction parallel to the molecular long axis direction. The transition electric dipole moment magnitude | My | in the direction perpendicular to the molecular long axis direction is greater than the magnitude | Mx | of the transition electric dipole moment parallel to the molecular long axis direction. Low molecular weight compounds.

In this specification, the “molecular long axis” of an organic compound is determined by density functional calculation using a computer. That is, an optimized structure of a molecule is obtained by density functional calculation, and an axis connecting two atoms having the longest distance among arbitrary two atom distances in the obtained molecular structure is defined as a molecular long axis. In the construction of this molecular structure, GausView 3.0 (manufactured by Gaussain Inc.) is used. As a program used for molecular structure optimization, Gaussian 03 Rev. is used. D. 02 (manufactured by Gaussain Inc.), B3LYP / 6-31G (d) is used as the basis function, and the default value is used as the convergence condition.
Further, the transition electric dipole moments Mx and My and their magnitudes | Mx | and | My |, and absorption wavelengths derived from Mx and My can be obtained by time-dependent density functional calculation. As a program used for time-dependent density functional calculation, Gaussian 03 Rev. D. 02 (manufactured by Gaussain Inc.), B3LYP / 6-31 + G (d) is used as a basis function, and a solvent effect is further introduced by the PCM method.
More specifically, from the inner product of the vector constituting the transition electric dipole moment obtained by the above calculation and the vector represented by the Cartesian coordinates of the atoms constituting both ends of the molecular long axis, the transition electric dipole moment and the above The angle formed with the molecular long axis is determined, and based on these, the molecular absorption wavelength derived from the Mx, My, and | Mx |, | My |, Mx, and My is determined.

  In the present invention, the term “transition electric dipole moment perpendicular to the molecular long axis direction” does not mean only the transition electric dipole moment that forms an angle of exactly 90 ° with the molecular long axis direction. In consideration of the angle deviation in the generally allowable range, the largest transition electric dipole moment among all-direction transition electric dipole moments that form an angle of 70 ° to 110 ° with the molecular major axis direction. Shall mean.

One of the characteristics of the compound (A) is that the molecular absorption wavelength derived from the transition electric dipole moment My in the direction orthogonal to the molecular long axis direction becomes the transition electric dipole moment Mx in the direction parallel to the molecular long axis direction. The wavelength is longer than the molecular absorption wavelength.
Here, the absorption wavelength derived from the transition electric dipole moment Mx orthogonal to the molecular long axis direction is about 10 nm to 200 nm longer than the absorption wavelength derived from the transition electric dipole moment My parallel to the molecular long axis direction. The long wavelength is preferably about 20 nm to 150 nm, more preferably about 30 nm to 120 nm. The absorption wavelength derived from the transition electric dipole moment My orthogonal to the major axis direction is preferably about 250 nm to 400 nm, more preferably about 300 nm to 380 nm, and further preferably about 320 nm to 375 nm. preferable.

  Another feature of the compound (A) is that the magnitude of the transition electric dipole moment | My | perpendicular to the molecular long axis direction is parallel to the molecular long axis direction | Greater than Mx |. That is, the ratio (| My | / | Mx |) of both is 1 or more, more preferably about 1 to 50, and further preferably about 1.1 to 30.

The compound (A) is preferably a low molecular compound. In the present specification, the “low molecular compound” means a compound having a molecular weight of 1500 or less. The molecular weight is more preferably 1200 or less, and even more preferably 1000 or less.
A compound having a molecular weight larger than the molecular weight within the above range is not preferred because it tends to cause bleed out.

By adding the compound (A) that satisfies the above conditions, it is possible to control the wavelength dispersion of the optical properties (particularly Re) of the optically anisotropic film. Note that the refractive index or birefringence of the optical anisotropic film varies depending on the light in the visible light range (that is, depending on the measurement wavelength). It is called wavelength dispersion, and in particular, it has the ability to increase the refractive index or birefringence of the optical anisotropic film as the wavelength becomes longer with respect to light in the visible light range, “having reverse wavelength dispersion”. Having a property that the refractive index or birefringence of the optically anisotropic film decreases as the wavelength increases with respect to light in the visible light region is referred to as “having forward wavelength dispersion”.
As an example of the use of the optically anisotropic film of the present invention, an optical film for a liquid crystal display device (particularly a VA mode liquid crystal display device) having an effect of reducing coloring when observed from an oblique direction during black display. There are uses. In this optical film, the in-plane retardation Re is preferably increased as the wavelength becomes longer with respect to light in the visible light range, that is, Re exhibits reverse wavelength dispersion. By forming the polymer composition containing the compound (A) that satisfies the above conditions together with the composite particles into a film shape and further subjecting to a stretching treatment as desired, the retardation expressed by the composite particles is visible. An optically anisotropic film exhibiting reverse wavelength dispersion characteristics in the light region can be produced.

In the film, the molecules of the material are generally oriented in a predetermined direction. The birefringence Δn of the film is a value obtained by subtracting the refractive index in the direction orthogonal to the direction (hereinafter referred to as MD direction) from the refractive index in the orientation direction (hereinafter referred to as TD direction). If the chromatic dispersion in the MD direction is more downward than the chromatic dispersion of the rate (the slope of Δn when the right is the long wavelength side and the left is the short wavelength side), the value obtained by subtracting that value, The birefringence Δn becomes inverse wavelength dispersion.
The wavelength dispersion of the refractive index is closely related to the absorption of the substance as represented by the Lorentz-Lorenz equation. Therefore, in order for the wavelength dispersion in the MD direction to be more downward, TD It is necessary that the absorption transition wavelength in the MD direction is longer than that in the direction. The compound (A) satisfying the above condition has an absorption transition wavelength that is a long wavelength in the polymer width direction (MD direction) due to its structural characteristics. As a result, the optically anisotropic film containing the compound is The reverse chromatic dispersion characteristics are shown for birefringence Δn.
More specifically, when the compound (A) is added to a polymer material and subjected to stretching treatment, the molecular long axis of the compound (A) is oriented in the TD direction. As described above, in the compound (A), the molecular absorption wavelength derived from the transition electric dipole moment My in the direction orthogonal to the molecular long axis direction is derived from the transition electric dipole moment Mx in the direction parallel to the molecular long axis direction. From the magnitude | Mx | of the transition electric dipole moment that is longer than the molecular absorption wavelength and that is in the direction perpendicular to the molecular long axis direction | My | large. For this reason, it is possible to make the absorption transition wavelength in the MD direction longer than that in the TD direction.

  Examples of the compound (A) that satisfies the above conditions include compounds represented by the following general formula (V), but are not limited thereto.

In the general formula (V), L ¹ and L ² each represent a single bond or a divalent linking group. B ¹ and B ² are groups selected from —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, and —CO—. R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each represent a substituent. n represents an integer of 0 to 2.

In the formula (V), L ¹ and L ² each preferably represent the following group.

  More preferred is —O—, —COO— or —OCO—.

R ⁴ is a substituent, and when a plurality of R ⁴ are present, they may be the same or different and may form a ring. As an example of the substituent, a substituent selected from the following substituent group Y is preferable.
Substituent group Y
A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert- Butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl) Group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. , Bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), alke Group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it is a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed, for example, a 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group (substituted or substituted). An unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), alkynyl group ( It is preferred, and a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, aromatic A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably Or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy. Group), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or non-substituted group having 2 to 30 carbon atoms Substituted heterocyclic oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as Formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, For example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxy Carbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group) An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxy Carbonyloxy group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonyl Mino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino Group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) An amino group such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, an mn-octyloxyphenoxycarbonylamino group, a sulfamoylamino group (preferably having 0 to 30 carbon atoms); Substituted or unsubstituted sulfamoylamino groups, such as sulfamoylamino groups, N, N-dimethylaminosulfonylamino groups, Nn-octylaminosulfonylamino groups, alkyl and arylsulfonylamino groups (preferably carbon A substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, 2, 3 , 5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group),

A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group or an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). A substituted arylthio group such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2 -Benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- ( 3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetate Rusulfamoyl group, N-benzoylsulfamoyl group, N- (N′phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably having 1 to 30 carbon atoms) A substituted or unsubstituted alkylsulfonyl group, 6-30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group), acyl group (preferably formyl) Group, A substituted or unsubstituted alkylcarbonyl group having 2 to 30 primes, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group or a pivaloylbenzoyl group, an aryloxycarbonyl group (preferably carbon A substituted or unsubstituted aryloxycarbonyl group of 7 to 30, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxycarbonyl group), alkoxycarbonyl group (preferably Is a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, or an n-octadecyloxycarbonyl group),

Carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, For example, phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably Is a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino group, diphenylphospho A fino group, a methylphenoxyphosphino group), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group), Phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group), phosphinylamino group (Preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group) and a silyl group (preferably having 3 to 3 carbon atoms) 30 substituted or unsubstituted silyl groups such as trimethylsilyl group, tert-butyldimethylsilyl , Phenyl dimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

R ⁴ is preferably a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group, or amino group, more preferably , A halogen atom, an alkyl group, a cyano group, or an alkoxy group.

R ⁵ and R ⁶ each represent a substituent. The substituent is preferably selected from the above substituent group Y. R ⁵ and R ⁶ are each preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexyl group. More preferred are a phenyl group having a substituent and a cyclohexyl group having a substituent, and further preferred is a bephenyl group having a substituent at the 4-position or a cyclohexyl group having a substituent at the 4-position.

R ⁷ and R ⁸ each represent a substituent. The substituent is preferably selected from the substituent group Y. R ⁷ and R ⁸ are preferably substituent constant sigma _p value of Hammett is greater than zero electron withdrawing group, sigma _p value has an electron withdrawing substituent of 0 to 1.5 More preferably. Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group. R ⁷ and R ⁸ may combine to form a ring.
As for Hammett's substituent constants σ _p and σ _m , for example, Naoki Inamoto's “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan “New Experimental Chemistry Course 14 Synthesis of Organic Compounds” Reaction V ”2605 (Maruzen), Tadao Nakaya“ Theoretical Organic Chemistry ”217 (Tokyo Kagaku Dojin), Chemical Review, 91, 165-195 (1991) .

B ¹ and B ² are groups selected from —O—, —NR— (R is a hydrogen atom or a substituent), —S—, and —CO—, respectively. Preferably, it is a group selected from -O-, -NR- (R is a substituent), and -S-.

  n is preferably 0 or 1, and most preferably 0.

  Hereinafter, although the specific example of the compound represented by the said general formula (V) which satisfies the conditions of the said compound (A) is shown, it is not limited to these. Regarding the following compounds, unless otherwise specified, the number in parentheses () indicates the exemplified compound (X).

  The synthesis of the compound represented by the general formula (V) can be performed with reference to a known method. For example, exemplary compound (16) of general formula (V) can be synthesized according to the following scheme.

In the above scheme, the synthesis from compound (1-A) to compound (1-D) is described in “Journal of Chemical Crystallography” (1997); 27 (9); p. 515-526. It can be performed with reference to the method described in 1.
Further, as shown in the above scheme, methanesulfonic acid chloride was added to a tetrahydrofuran solution of the compound (1-E), N, N-diisopropylethylamine was added dropwise and stirred, and then N, N-diisopropylethylamine was added. Exemplary tetrahydrofuran (16) can be obtained by adding dropwise a tetrahydrofuran solution of compound (1-D) and then adding a tetrahydrofuran solution of N, N-dimethylaminopyridine (DMAP).

Another example of the compound (A) is an anthraquinone derivative.
Examples of the anthraquinone derivative that can be used as the compound (A) include, but are not limited to, the following compounds.

  The compound (A) preferably exhibits a liquid crystal phase in a temperature range of 100 ° C to 300 ° C. More preferably, it is 120 degreeC-200 degreeC. The liquid crystal phase is preferably a nematic phase or a smectic phase.

  In the optically anisotropic film of the present invention, the content of the compound (A) is preferably 0.1 to 30 parts by mass with respect to the polymer material (preferably cellulose acylate), 0.5 to It is more preferably 20 parts by mass, further preferably 1 to 12 parts by mass, and further preferably 1 to 5 parts by mass.

[Other additives]
Examples of additives that are optionally added to the optically anisotropic film of the present invention include ultraviolet light inhibitors, plasticizers, deterioration inhibitors, fine particles (however, not including the above composite particles), optical property adjusting agents, and the like. Is included.

[Ultraviolet absorber]
The optically anisotropic film of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, any type can be selected according to the purpose, and a salicylic acid ester-based, benzophenone-based, benzotriazole-based, benzoate-based, cyanoacrylate-based, nickel complex-based absorber or the like is used. Preferred are benzophenone series, benzotriazole series, and salicylic acid ester series.

  Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-di-hydroxy-4-methoxybenzophenone, 2, 2′-di-hydroxy-4,4′-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4- (2-hydroxy-3- And methacryloxy) propoxybenzophenone.

  As the benzotriazole ultraviolet absorber, 2 (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2 (2′-hydroxy-5′-tert-butylphenyl) ) Benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5 And chlorobenzotriazole, 2 (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, and the like.

  Examples of salicylic acid esters include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

  Among these exemplified ultraviolet absorbers, in particular, 2-hydroxy-4-methoxybenzophenone, 2,2′-di-hydroxy-4,4′-methoxybenzophenone, 2 (2′-hydroxy-3′-tert-butyl- 5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) ) Benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole is particularly preferred.

  As the ultraviolet absorber, it is preferable to use a combination of a plurality of absorbers having different absorption wavelengths because a high blocking effect can be obtained in a wide wavelength range. When the optically anisotropic film of the present invention is used as an optical film of a liquid crystal display device, the ultraviolet absorber is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and has a liquid crystal display property from the viewpoint of preventing deterioration of the liquid crystal. From the viewpoint, those that absorb less visible light having a wavelength of 400 nm or more are preferable. Particularly preferred ultraviolet absorbers are the above-described benzotriazole compounds, benzophenone compounds, and salicylic acid ester compounds. Among these, a benzotriazole-based compound is preferable because unnecessary coloring with respect to the cellulose ester is small.

  As for the UV absorber, JP-A-60-235852, JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, JP-A-6-107854. 118233, 6-148430, 7-11056, 7-11055, 7-11056, 8-29619, 8-239509, JP-A-2000-204173 These compounds can also be used.

  The addition amount of the ultraviolet absorber is preferably 0.001 to 5% by mass, and more preferably 0.01 to 1% by mass with respect to the polymer material (preferably cellulose acylate). If the addition amount is 0.001% by mass or more, the effect of addition can be sufficiently exerted, and if the addition amount is 5% by mass or less, for example, the ultraviolet absorber bleeds out to the optically anisotropic film surface. Is preferable.

[Deterioration inhibitor]
The optically anisotropic film of the present invention may contain a deterioration inhibitor. The deterioration inhibitor may be added for the purpose of preventing the polymer material such as cellulose acylate from deteriorating and decomposing. Examples of the deterioration preventing agent include butylamine, hindered amine compounds (JP-A-8-325537), guanidine compounds (JP-A-5-271471), benzotriazole-based UV absorbers (JP-A-6-235819), and benzophenone-based compounds. A compound such as a UV absorber (JP-A-6-118233) can be used.

[Plasticizer]
The optically anisotropic film of the present invention may contain a plasticizer. The plasticizer is preferably a phosphate ester and / or a carboxylate ester. As the phosphate ester plasticizer, for example, triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate (BDP), trioctyl phosphate, tributyl phosphate and the like are preferable. . Examples of the carboxylic acid ester plasticizer include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP), diethyl hexyl phthalate (DEHP), O -Triethyl acetyl citrate (OACTE), tributyl O-acetyl citrate (OACTB), acetyl triethyl citrate, acetyl tributyl citrate, butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, triacetin, tributyrin, butyl phthalyl butyl Glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and the like are preferable. Furthermore, the plasticizer is preferably (di) pentaerythritol esters, glycerol esters, diglycerol esters.

[Peeling accelerator]
The optically anisotropic film of the present invention may contain a peeling accelerator depending on the application. Preferred examples of the peeling accelerator include citric acid ethyl esters.

[Infrared absorber]
The optically anisotropic film of the present invention may contain an infrared absorber depending on the application. As the infrared absorber, for example, those described in JP-A No. 2001-194522 are preferable.

[dye]
The optically anisotropic film of the present invention may contain a dye for adjusting the hue. The content of the dye is preferably 10 to 1000 ppm, more preferably 50 to 500 ppm in terms of a mass ratio with respect to the polymer material such as cellulose acylate. By including the dye in this manner, for example, when the optically anisotropic film of the present invention is produced, light piping can be reduced and yellowness can be improved.

[Matting agent fine particles]
The optically anisotropic film of the present invention may contain matting agent fine particles. Fine particles that can be used as a matting agent include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. As the fine particles, those containing silicon are more preferable from the viewpoint of low turbidity, and silicon dioxide is particularly preferable. The fine particles of silicon dioxide preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. Those having an average primary particle size as small as 5 to 16 nm can reduce the haze of the film, and are more preferable. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.
In the case of the present invention, since it contains smectite or mica on which molecules having an adsorbing group to inorganic particles are adsorbed, if such smectite or mica also functions as a matting agent, it is not necessary to add a matting agent separately. However, the same effect may be obtained.

  These fine particles usually form secondary particles having an average particle size of 0.1 to 3.0 μm, and these fine particles exist in the film as aggregates of primary particles, and 0.1 to 0.1 μm on the film surface. An unevenness of 3.0 μm is formed. The secondary average particle size is preferably 0.2 μm to 1.5 μm, more preferably 0.4 μm to 1.2 μm, and most preferably 0.6 μm to 1.1 μm. For the primary / secondary particle size, the particles in the film were observed with a scanning electron microscope, and the diameter of the circle circumscribing the particles was defined as the particle size. In addition, 200 particles were observed at different locations, and the average value was taken as the average particle size.

  As the silicon dioxide fine particles, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (all of which are trade names, manufactured by Nippon Aerosil Co., Ltd.) are used. be able to. Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (all of which are trade names, manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. This is particularly preferable because the effect of reducing the coefficient is great.

[Rate of compound addition]
In the optically anisotropic film of the present invention, the total amount of compounds having a molecular weight of 3000 or less is preferably 5 to 45% by mass with respect to the mass of the polymer material such as cellulose acylate. More preferably, it is 10-40 mass%, More preferably, it is 15-30 mass%. These compounds include the above-described compounds adsorbed on smectite or mica, and Re enhancers, UV inhibitors, plasticizers, deterioration inhibitors, fine particles, release agents, infrared absorbers, and the like, which are added as desired. Furthermore, the total amount of compounds having a molecular weight of 2000 or less is more preferably within the above range. By setting the total amount of these compounds to 5% by mass or more, it becomes difficult for the properties of a single polymer material such as cellulose acylate to appear, and for example, optical performance and physical strength are less likely to fluctuate with changes in temperature and humidity. Become. Moreover, by setting the total amount of these compounds to 45% by mass or less, it exceeds the limit of compatibility of the compound in a polymer film such as a cellulose acylate film, and is deposited on the film surface to cause clouding of the film (crying from the film) ) Is preferred because it tends to be suppressed.

  In addition, the additive that is optionally added to the optically anisotropic film of the present invention may be solid or oily. The melting point and boiling point are not particularly limited. For example, a UV absorber at 20 ° C. or lower and a UV absorber at 20 ° C. or higher can be mixed and used, or a plasticizer can be mixed and used. Specifically, the method described in JP 2001-151901 A can be employed.

[Preparation Example of Optically Anisotropic Film of the Present Invention]
When cellulose acylate is used as the polymer material, the optically anisotropic film of the present invention can be prepared, for example, by the following method.
First, a cellulose acylate solution is prepared, and the composite particles are added to the solution. In addition, various additives (for example, a Re developing agent, an ultraviolet light inhibitor, a plasticizer, a deterioration preventing agent, fine particles, an optical property adjusting agent, etc.) can be added as necessary. There is no particular limitation on the addition timing of the composite particles and other additives. You may add simultaneously, and you may add either first.

An example of a preferable method for producing the optically anisotropic film of the present invention includes a method of preparing a dope of a polymer material containing the composite particles and molding the dope into a film by a solvent cast method. Hereinafter, an example in which an optically anisotropic film is produced by a solvent cast method when the polymer material is cellulose acylate will be described.
First, a cellulose acylate solution is prepared. As the main solvent used for the preparation of the dope, a solvent selected from esters having 3 to 12 carbon atoms, ketones, ethers, and halogenated hydrocarbons having 1 to 7 carbon atoms is preferable. Esters, ketones and ethers may have a cyclic structure. A compound having two or more functional groups of esters, ketones and ethers (that is, —O—, —CO— and —COO—) can also be used as a main solvent. It may have a functional group of In the case of the main solvent having two or more kinds of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

  Further, chlorinated halogenated hydrocarbons may be used as the main solvent, and as described in, for example, published technique (published technical report 2001-1745, pages 12-16, issued in 2001, Japan Invention Association) A chlorinated solvent may be used as the main solvent.

In addition, about the preparation method of the cellulose acylate solution used for a solvent cast method, for example, the kind of solvent used, its dissolution method, etc., what is indicated by the following patent documents can be mentioned as a preferable aspect.
JP 2000-95876 A, JP 12-95877 A, JP 10-324774 A, JP 8-152514 A, JP 10-330538 A, JP 9-95538 A, JP 9-95557 A, Special Kaihei 10-235664, JP-A-12-63534, JP-A-11-21379, JP-A-10-182853, JP-A-10-278056, JP-A-10-279702, JP-A-10-323853, JP-A-10-323853 JP-A-10-237186, JP-A-11-60807, JP-A-11-152342, JP-A-11-292988, JP-A-11-60752, and JP-A-11-60752.
These patent documents describe not only the preferable solvent used for the preparation of the cellulose acylate solution, but also the physical properties of the solution and the coexisting substances to be coexisted, which are also preferable embodiments in the present invention.

In the dope, the composite particles and additives that are optionally added are added. These agents may be added at any time during the dope preparation step, and these additives may be added at the end of the dope preparation step.
For example, the ultraviolet absorber may be added simultaneously when dissolving the cellulose acylate, or may be added to the dope after dissolution. In particular, a mode in which an ultraviolet absorbent solution is added to the dope immediately before casting using a static mixer or the like is preferable because spectral absorption characteristics can be easily adjusted. Similarly, when a dye is contained in the film, it may be added together with the cellulose acylate or the solvent during the preparation of the cellulose acylate solution, or may be added during or after the solution preparation. Moreover, you may add to the ultraviolet absorber liquid added in-line. The dyes described in JP-A-5-34858 can be used.

In order to obtain a cellulose acylate film having particles having a small secondary average particle size of inorganic fine particles in the film, several methods are conceivable when preparing a dispersion of inorganic fine particles. For example, a method of preparing a fine particle dispersion in which a solvent and fine particles are stirred and mixed in advance, adding the fine particle dispersion to a small amount of a separately prepared cellulose acylate solution, stirring and dissolving, and further mixing with a main cellulose acylate dope solution There is.
This method is a preferable preparation method in that the dispersibility of the inorganic fine particles is good and the fine particles are more difficult to reaggregate. In addition, after adding a small amount of cellulose ester to the solvent and dissolving with stirring, add the fine particles to this and disperse with a disperser, and use this as a fine particle additive solution. There is also a method of mixing. Although the present invention is not limited to these methods, the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed as a matting agent with a solvent is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, 15-20 mass% is still more preferable. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and 0.08 to 0.16 g per 1 m ^2. Even more preferred.
The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

(Dissolution process)
As a method for preparing the cellulose acylate solution (dope), various dissolution methods can be used. The dissolution may be performed at room temperature, and further, a cooling dissolution method or a high temperature dissolution method may be used. Furthermore, dissolution may be carried out by combining these. Regarding the preparation method of the cellulose acylate solution, and each step of solution concentration and filtration accompanying the dissolution step, JIII Journal of Technical Disclosure (Technical No. 2001-1745, pages 22-25, published on March 15, 2001, The manufacturing process described in detail in the “Invention Association” is preferably used.

  The dope transparency of the cellulose acylate solution is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more. As a specific method for calculating the dope transparency, the dope solution is injected into a 1 cm square glass cell, and the absorbance at 550 nm is measured with a spectrophotometer (UV-3150, trade name, Shimadzu Corporation). Only the solvent is measured in advance as a blank, and the transparency of the cellulose acylate solution is calculated from the ratio to the absorbance of the blank.

(Casting, drying, winding process)
Next, the prepared cellulose acylate solution is cast and formed into a film. As a method and equipment for producing a cellulose acylate film, a solution casting film forming method and a solution casting film forming apparatus conventionally used for producing a cellulose triacetate film can be widely adopted. Specifically, first, a dope (cellulose acylate solution) prepared from a dissolving machine (pot) is temporarily stored in a storage pot, and bubbles contained in the dope are defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of revolutions, and the dope is run endlessly from the die (slit) of the pressure die. The dope film (also referred to as a web) is peeled off from the metal support at the peeling point where the metal support is cast almost uniformly around the metal support. The both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width and dried, and then the obtained film is mechanically transported by a roll group of a drying device, dried, and then rolled by a winder. Wind up to a predetermined length. The combination of the tenter and the roll group dryer varies depending on the purpose.

  For example, when the produced cellulose acylate film is used for an optical compensation film and a polarizing plate protective film, which are optical members for an electronic display, and a silver halide photographic light-sensitive material, in addition to a usual solution casting film forming apparatus. In addition, a coating apparatus is often added for surface processing on films such as an undercoat layer, an antistatic layer, an antihalation layer, and a protective layer. These are described in detail in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, pages 25-30, published on March 15, 2001, Japan Institute of Invention), and include casting (including co-casting). ), Metal support, drying, peeling, etc., and can be preferably used in the present invention.

[Stretching treatment]
In this manner, the optically anisotropic film of the present invention can be produced using a solvent cast method or the like. When the produced optically anisotropic film (for example, cellulose acylate film) has desired optical properties, it can be used for a predetermined application as it is. Further, in order to obtain desired optical characteristics, a stretching process may be further performed. In particular, when the in-plane retardation value of the cellulose acylate film is set to a high value, a method of positively stretching in the width direction, for example, JP-A-62-115035, JP-A-4-152125, The stretching treatment can be performed by a method of stretching the produced film described in JP-A-4-284211, JP-A-4-298310, and JP-A-11-48271.

  The film is stretched at room temperature or under heating conditions. The heating temperature is preferably not higher than the glass transition temperature of the film. The stretching of the film may be uniaxial stretching only in the longitudinal or lateral direction, or may be simultaneous or sequential biaxial stretching. The film is preferably stretched by 1 to 200%, more preferably stretched by 1 to 100%, and further preferably stretched by 1 to 50%.

  When the optically anisotropic film produced by the above method is used as a polarizing plate as a protective film for a polarizing film, etc., in order to suppress light leakage when the produced polarizing plate is observed obliquely Needs to arrange the transmission axis of the polarizing film and the slow axis in the plane of the optically anisotropic film in parallel. Since the transmission axis of the roll film-shaped polarizing film produced continuously is generally parallel to the width direction of the roll film, the roll film-shaped polarizing film and the roll film-shaped optical anisotropic film In order to continuously bond a certain protective film, the in-plane slow axis of the roll film-shaped protective film needs to be parallel to the width direction of the film. Therefore, it is preferable to stretch more in the width direction. The stretching process may be performed in the middle of the film forming process, or the original fabric that has been formed and wound may be stretched. In the former case, stretching may be performed in a state containing a residual solvent, and the stretching can be preferably performed at a residual solvent amount of 2 to 30% by mass.

  The preferred range of the thickness of the optically anisotropic film obtained after drying varies depending on the purpose of use, but generally it is preferably in the range of 5 to 500 μm, more preferably in the range of 20 to 300 μm. More preferably, it is in the range of 30 to 150 μm. Moreover, it is preferable that it is 40-110 micrometers for optical use, especially for VA liquid crystal display devices. The film thickness may be adjusted by adjusting the solid content concentration contained in the dope, the slit gap of the die base, the extrusion pressure from the die, the metal support speed, and the like so as to obtain a desired thickness.

  The form of the optically anisotropic film produced through the above solvent cast method and the stretching process carried out as desired is a long form and a form wound up in a roll shape. In this embodiment, the width is preferably 0.5 to 3 m, more preferably 0.6 to 2.5 m, and still more preferably 0.8 to 2.2 m. The length is preferably 100 to 10,000 m per roll, more preferably 500 to 7000 m, and still more preferably 1000 to 6000 m. When winding, it is preferable to give knurling to at least one end, the knurling width is preferably 3 mm to 50 mm, more preferably 5 mm to 30 mm, and the height is preferably 0.5 to 500 μm, more preferably 1 to 200 μm. is there. This may be a single push or a double push.

  The variation in the Re (590) value (= Re value at a wavelength of 590 nm) in the width direction of the optically anisotropic film is preferably ± 5 nm, and more preferably ± 3 nm. The variation in the Rth (590) value in the width direction (= Rth value at a wavelength of 590 nm) is preferably ± 10 nm, and more preferably ± 5 nm. Moreover, it is preferable that the variation in the Re value and the Rth value in the length direction is also within the range of the variation in the width direction.

  In order to control the Re value and Rth value of the optically anisotropic film of the present invention within preferable ranges, the type and amount of the molecule adsorbed on the smectite or mica used, and the stretching ratio of the film are appropriately adjusted. It is preferable to do.

Hereinafter, the preferable range of the characteristics of the optically anisotropic film of the present invention will be described depending on the application.
[Optical characteristics of optically anisotropic film]
In the present specification, Re (λ) and Rth (λ) represent in-plane retardation (nm) and retardation in the thickness direction (nm) at wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the optically anisotropic film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).
When the optically anisotropic film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis). An arbitrary direction in the plane is set as the rotation axis), and light of wavelength λ nm is incident from the inclined direction to the normal direction of the optical anisotropic film from the normal direction to 50 degrees on one side in 10 degree steps. A total of 6 points are measured, and KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed average refractive index, and the input film thickness value.
In the above case, in the case of an optically anisotropic film having a retardation value of zero at a certain tilt angle with the in-plane slow axis as the rotation axis from the normal direction, the tilt angle is larger than the tilt angle. The retardation value is calculated by KOBRA 21ADH or WR after changing the sign to negative.

  Note that the retardation value is obtained from any two inclined directions with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the optical anisotropic film surface is the rotation axis). Rth can also be calculated from the following formula (1) and formula (2) based on the measured value, the assumed value of the average refractive index, and the input film thickness value.

注記：
式中、Ｒｅ（θ）は法線方向から角度θ傾斜した方向におけるレターデーション値を表す。
式中、ｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表す。ｄは光学異方性膜の膜厚を表す。

Note:
In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In the formula, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents the film thickness of the optically anisotropic film.

When the optically anisotropic film to be measured is a film that cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film without a so-called optical axis, Rth (λ) is calculated by the following method. The
Rth (λ) is −50 with respect to the normal direction of the optically anisotropic film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) and the tilt axis (rotation axis). 11 points of light having a wavelength of λ nm are incident from 10 degrees from +50 degrees to 10 degrees in each step, and the measured retardation value, the assumed average refractive index and the input film thickness value are measured. Based on KOBRA 21ADH or WR.
In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59). The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

The optical characteristics required for the optical compensation film differ depending on which mode of the liquid crystal display device is used.
For the OCB mode, Re (550) is preferably 10 to 100 nm, more preferably 20 to 70 nm in view of widening the viewing angle. Rth (550) is preferably 50 to 300 nm, more preferably 100 to 250 nm.
From the same viewpoint, for TN, Re (550) is preferably 0 to 50 nm, more preferably 2 to 30 nm. Rth (550) is preferably 10 to 200 nm, more preferably 30 to 150 nm.
In the OCB mode and the TN mode, another optical anisotropic film can be applied on the optical anisotropic film having the retardation value and used as an optical compensation film.

  When the optically anisotropic film of the present invention is used for the VA mode, a mode in which a total of two sheets are used on both sides of the cell (two-sheet type) and a mode in which only one of the upper and lower sides of the cell is used Preferred optical characteristics are different in two types (single-sheet type).

  In the case of the single sheet type used for the VA mode or the IPS mode, Re (550) is preferably 30 to 150 nm, and more preferably 40 to 100 nm. Rth (550) is preferably from 100 to 300 nm, more preferably from 150 to 250 nm.

  When used on both sides of a liquid crystal cell as an optical compensation sheet for a VA liquid crystal display device and used as a two-sheet type, Re (550) is in the range of 20 to 100 nm and Rth (550) is in the range of 100 to 200 nm. Preferably, Re (550) is 25 to 80 nm and Rth (550) is 100 to 150 nm.

In particular, when used as a two-sheet type, the optically anisotropic film of the present invention preferably satisfies the following formulas (A) to (D) from the viewpoint of improving the aforementioned color shift problem.
(A) 0.1 <Re (450) / Re (550) <0.95
(B) 1.03 <Re (650) / Re (550) <1.93
(C) 0.4 <(Re / Rth (450)) / (Re / Rth (550)) <0.95
(D) 1.05 <(Re / Rth (650)) / (Re / Rth (550)) <1.9
(Where Re (λ) is the in-plane retardation value of the optically anisotropic film with respect to light of wavelength λnm, and Rth (λ) is the thickness direction of the optically anisotropic film with respect to light of wavelength λnm. Re / Rth (λ) is the ratio of the in-plane retardation value of the optically anisotropic film to the retardation value in the thickness direction with respect to light having a wavelength of λ nm (unit: nm).

The optically anisotropic film of the present invention satisfying the above formulas (A) to (D) can also be used as a single sheet used for the VA mode from the same viewpoint.
Furthermore, when using the optically anisotropic film of the present invention satisfying the above formulas (A) to (D) as a single sheet, it is more preferable to satisfy the following formulas (A1) to (D1).
(A1) 0.4 <Re (450) / Re (550) <0.95
(B1) 1.05 <Re (650) / Re (550) <1.93
(C1) 0.45 <(Re / Rth (450)) / (Re / Rth (550)) <0.95
(D1) 1.05 <(Re / Rth (650)) / (Re / Rth (550)) <1.7

Further, it is more preferable to satisfy the following formulas (A2) to (D2).
(A2) 0.5 <Re (450) / Re (550) <0.95
(B2) 1.10 <Re (650) / Re (550) <1.93
(C2) 0.50 <(Re / Rth (450)) / (Re / Rth (550)) <0.95
(D2) 1.05 <(Re / Rth (650)) / (Re / Rth (550)) <1.5

[surface treatment]
The optically anisotropic film of the present invention may be subjected to a surface treatment as desired to improve the adhesion between the optically anisotropic film and other functional layers (for example, an undercoat layer and a back layer). For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs under a low pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferred. A plasma-excitable gas is a gas that is plasma-excited under the above conditions, and includes chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, pages 30 to 32, issued on March 15, 2001, Invention Association), and preferably used in the present invention. Can do.

[Alkaline saponification]
The alkali saponification treatment is particularly effective when the polymer material is cellulose acylate. It is preferable to carry out the method by directly immersing the optically anisotropic film in a saponifying solution tank or by applying the saponifying solution to the optically anisotropic film. Examples of the coating method include a dip coating method, a curtain coating method, an extrusion coating method, a bar coating method, and an E-type coating method. The solvent of the alkali saponification treatment coating solution has good wettability because the saponification solution is applied to the optically anisotropic film, and the surface of the optically anisotropic film surface is not formed by the saponification solution solvent. It is preferable to select a solvent that keeps the shape good. Specifically, an alcohol solvent is preferable, and isopropyl alcohol is particularly preferable. An aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkali saponification coating solution is preferably an alkali that dissolves in the above solvent, and more preferably KOH or NaOH. The pH of the saponification coating solution is preferably 10 or more, more preferably 12 or more. The reaction conditions at the time of alkali saponification are preferably 1 second to 5 minutes at room temperature, more preferably 5 seconds to 5 minutes, and particularly preferably 20 seconds to 3 minutes. After the alkali saponification reaction, it is preferable to wash the surface on which the saponification solution is applied with water or with an acid and then with water.

  The optically anisotropic film of the present invention can be used as a member in various fields. Particularly suitable for optical materials and photographic light-sensitive materials. In particular, it is suitable as an optical film for liquid crystal display devices. It is preferable as an optical compensation film for compensating the birefringence of a liquid crystal cell and as a protective film for a polarizing film.

  When the optically anisotropic film of the present invention is used as an optical film of a liquid crystal display device, various functional layers may be applied to the film. These include, for example, an antistatic layer, a cured resin layer (transparent hard coat layer), an antireflection layer, an easy adhesion layer, an antiglare layer, an optical compensation layer, an alignment layer, a liquid crystal cured layer, and the like. Examples of the functional layer and the material thereof include surfactants, slip agents, matting agents, antistatic agents, materials for hard coat layers, and the like. Page, published on March 15, 2001, Invention Association), and can be preferably used in the present invention.

[Polarizer]
The film of the present invention (preferably a cellulose film) is particularly useful as a polarizing plate protective film. When using as a polarizing plate protective film, the manufacturing method of a polarizing plate is not specifically limited, It can manufacture by a general method. There is a method in which the obtained film is treated with an alkali and bonded to both surfaces of a polarizing film prepared by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. Instead of alkali treatment, easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232 may be performed.
Examples of the adhesive used to bond the treated surface of the optically anisotropic film of the present invention and the polarizing film include, for example, polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl resins such as butyl acrylate. Examples include latex.
The polarizing plate is composed of a polarizing film and protective films that protect both surfaces thereof, and may further be configured by bonding a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the adhesive layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate.

  In a liquid crystal display device, a substrate containing liquid crystal is usually disposed between two polarizing plates. When a polarizing plate having an optically anisotropic film of the present invention is incorporated in a liquid crystal display device, the optically anisotropic film However, the optically anisotropic film of the present invention is preferably arranged between the liquid crystal cell and the polarizing film.

[Optical compensation film (retardation plate)]
The optically anisotropic film of the present invention is useful as an optical compensation film for liquid crystal display devices. The optical compensation film generally refers to an optical material that is used in a liquid crystal display device and compensates for the birefringence of a liquid crystal layer, and is synonymous with a retardation plate, an optical compensation sheet, and the like. The optical compensation film has birefringence and is used for the purpose of removing the color of the display screen of the liquid crystal display device or improving the viewing angle characteristics. The range of optical characteristics required for the optical compensation film used in the liquid crystal display device of each mode is as described above. The optically anisotropic film of the present invention becomes an optically anisotropic film that satisfies the above optical characteristics by adjusting the material and the amount of addition thereof and / or by stretching.

[Liquid Crystal Display]
The present invention also relates to a liquid crystal display device having the optically anisotropic film of the present invention and / or the polarizing plate of the present invention.
A liquid crystal display device usually has a liquid crystal cell that carries liquid crystal between two electrode substrates, and two polarizing films disposed on both sides thereof. The optically anisotropic film of the present invention is preferably used as an optical compensation film disposed between the liquid crystal cell and the polarizing film or as a polarizing film protective film.
The liquid crystal display device according to the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching Crystal), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroelectric Liquid Crystal), OCB (Optical Liquid Crystal). ), ECB (Electrically Controlled Birefringence), VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) liquid crystal display devices in any mode. A liquid crystal display device having a multi-domain structure may be used, and any of a transmissive, reflective, and transflective liquid crystal display device may be used.

(TN type liquid crystal display device)
The optically anisotropic film of the present invention may be used as an optical compensation sheet of a TN liquid crystal display device having a TN mode liquid crystal cell, as a part of the support, or as a protective film of a polarizing plate. TN mode liquid crystal cells and TN type liquid crystal display devices have been well known for a long time. The optical compensation sheet used in the TN type liquid crystal display device can be produced according to the descriptions in JP-A-3-9325, JP-A-6-148429, JP-A-8-50206, and JP-A-9-26572. it can. Further, according to the description of Mori et al. (Jpn. J. Appl. Phys. Vol. 36 (1997) p. 143 and Jpn. J. Appl. Phys. Vol. 36 (1997) p. 1068). Can be produced.

(STN type liquid crystal display device)
The optically anisotropic film of the present invention may be used as an optical compensation sheet of an STN type liquid crystal display device having an STN mode liquid crystal cell, as a part of the support, or as a protective film of a polarizing plate. In general, in a STN type liquid crystal display device, rod-like liquid crystalline molecules in a liquid crystal cell are twisted in the range of 90 to 360 degrees, and the refractive index anisotropy (Δn) and cell gap (d) of the rod-like liquid crystalline molecules. Product (Δnd) is in the range of 300 to 1500 nm. The optical compensation sheet used in the STN type liquid crystal display device can be manufactured according to the description in JP-A-2000-105316.

(VA type liquid crystal display device)
The optically anisotropic film of the present invention is particularly advantageously used as an optical compensation sheet of a VA liquid crystal display device having a VA mode liquid crystal cell, as a part of a support thereof, or as a protective film of a polarizing plate. The Re value of the optical compensation sheet used in the VA liquid crystal display device is preferably 0 to 150 nm and the Rth value is preferably 70 to 400 nm. When two optically anisotropic polymer films are used for the VA liquid crystal display device, the Rth value of the film is preferably 70 to 250 nm. When one optically anisotropic polymer film is used for the VA liquid crystal display device, the Rth value of the film is preferably 150 to 400 nm. The VA-type liquid crystal display device may be an alignment-divided system as described in, for example, JP-A-10-123576.

(IPS liquid crystal display device and ECB liquid crystal display device)
The optically anisotropic film of the present invention is an IPS type liquid crystal display device having IPS mode and ECB mode liquid crystal cells and an optical compensation sheet for an ECB type liquid crystal display device. Can also be used advantageously. In these modes, the liquid crystal material is aligned substantially in parallel during black display, and black is displayed by aligning liquid crystal molecules in parallel with the substrate surface in the absence of applied voltage. In these embodiments, the polarizing plate using the optically anisotropic film contributes to the improvement of the tint, the expansion of the viewing angle, and the improvement of the contrast. In this embodiment, the optically anisotropic film is used as a protective film (cell-side protective film) disposed between the liquid crystal cell and the polarizing plate among the protective films of the polarizing plates above and below the liquid crystal cell. It is preferable to use a polarizing plate on at least one side. More preferably, an optically anisotropic film is disposed between the protective film of the polarizing plate and the liquid crystal cell, and the retardation value of the disposed optically anisotropic film is not more than twice the value of Δn · d of the liquid crystal layer. It is preferable to set to.

(OCB type liquid crystal display device and HAN type liquid crystal display device)
The optically anisotropic film of the present invention is used as an optical compensation sheet of an OCB type liquid crystal display device having an OCB mode liquid crystal cell or a HAN type liquid crystal display device having a HAN mode liquid crystal cell, as a part of a support thereof, or It is also advantageously used as a protective film for a polarizing plate. In the optical compensation sheet used for the OCB type liquid crystal display device or the HAN type liquid crystal display device, it is preferable that the direction in which the absolute value of the retardation value is minimum does not exist in the plane of the optical compensation sheet or in the normal direction. The optical properties of the optical compensation sheet used in the OCB type liquid crystal display device or the HAN type liquid crystal display device are also the optical properties of the optically anisotropic layer, the optical properties of the support, and the optically anisotropic layer and the support. Is determined by the arrangement of An optical compensation sheet used for an OCB type liquid crystal display device or a HAN type liquid crystal display device can be produced according to the description in JP-A-9-197397. It can also be prepared according to the description of Mori et al. (Jpn. J. Appl. Phys. Vol. 38 (1999) p. 2837).

(Reflective liquid crystal display)
The optically anisotropic film of the present invention is also advantageously used as an optical compensation sheet of a TN type, STN type, HAN type, GH (Guest-Host) type reflective liquid crystal display device or the like. These display modes have been well known since ancient times. The TN-type reflective liquid crystal display device can be manufactured according to the descriptions in JP-A-10-123478, International Publication WO98 / 48320, and Patent Registration No. 3022477. The optical compensation sheet used in the reflective liquid crystal display device can be produced according to the description in the pamphlet of International Publication WO00 / 65384.

(Other liquid crystal display devices)
The optically anisotropic film of the present invention is also advantageously used as an optical compensation sheet or the like of an ASM type liquid crystal display device having a liquid crystal cell of ASM (Axial Symmetrical Aligned Microcell) mode. The ASM mode liquid crystal cell is characterized in that the thickness of the cell is maintained by a resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. An ASM mode liquid crystal cell and an ASM type liquid crystal display device can be manufactured in accordance with the description of Kume et al. (Kume et al., SID 98 Digest 1089 (1998)).

  When the optically anisotropic film of the present invention is used as an optical film for a liquid crystal display device, the display mode is more preferably a VA type.

[Other uses]
(Hard coat film, antiglare film, antireflection film)
The optically anisotropic film of the present invention can be preferably used as a coated film, an antiglare film or an antireflection film. For the purpose of improving the visibility of flat panel displays such as LCD, PDP, CRT, EL, etc., any or all of a hard coat layer, an antiglare layer and an antireflection layer can be applied to one or both sides of the film. . A preferred embodiment of such an antiglare film or antireflection film is described in detail in JIII Journal of Technical Disclosure (Technology No. 2001-1745, pages 54 to 57, issued on March 15, 2001, Invention Association). The film can be preferably used.

  The optically anisotropic film of the present invention is not limited to the above applications, and is used for producing display materials, optoelectronic materials, photonics materials, and the like.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

[Example 1]
(Preparation of composite particles)
No. shown in Table 1 below. In 4A, 6A, 8A, and 10A, composite particles prepared as follows were used as retardation adjusting agents.
50 parts by volume of methanol is added to commercially available synthetic smectite fine particles (trade name: Lucentite SPN; manufactured by Co-op Chemical Co., Ltd .; primary particle aspect ratio≈50 (thickness≈1 nm, particle diameter≈50 nm)), After stirring for 30 minutes at room temperature, ultrasonic treatment was performed for 30 minutes to prepare a uniform methanol dispersion. To the methanol dispersion, a 2.0% by mass methanol solution of a compound having an adsorbing group for inorganic particles (Exemplary compounds Q′-8, S-8, U-7, V-4) was added to a methanol dispersion of smectite. The same mass was gradually added while stirring. The aggregate is separated by solid-liquid separation by centrifugation (3000 rpm, 5 minutes), and 50 parts by mass of methylene chloride is added with respect to the mass of the smectite fine particles, followed by stirring at room temperature for 30 minutes, and then ultrasonication for 30 minutes. Processing was performed to obtain a uniform methylene chloride dispersion.
No. shown in Table 1 below. As the retardation adjusting agent of 5A, 7A, 9A, and 11A, synthetic mica fine particles (trade name: Somasif MPE; manufactured by Co-op Chemical Co., Ltd .; primary particle aspect ratio≈5000 (thickness≈1 nm, Composite particles prepared in the same manner as described above were used except that the particle size was about 5 μm)).
The amount of adsorbed molecules of the compound was quantified by ultraviolet-visible absorption spectrum and thermal analysis (TG / DTA), and the amount of adsorption (mass% per total mass of adsorbed smectite particles / mica particles) was It was found that it was as follows.
Adsorption amount to smectite particles:
Q'-8: 20.0%
S-8: 18.2%
U-7: 21.2%
V-4: 24.6%
Adsorption on mica particles:
Q'-8: 18.8%
S-8: 17.5%
U-7: 19.8%
V-4: 21.2%

  In addition, sample No. shown in Table 1 In Examples 12A to 15A, Exemplified Compounds Q-8, S-8, U-7, and V-4 were used without being adsorbed on smectite. The value was made the same as the value obtained by multiplying the added amount of the composite particles of 4A, 6A, 8A, and 10A by the calculated adsorption amount.

(Production of optically anisotropic film (cellulose acetate film samples No. 1A to 15A))
Each component of the following cellulose acetate solution composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
(Cellulose acetate solution composition)
Cellulose acetate having a degree of acetylation of 60.9% (degree of polymerization: 300) 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 318 parts by mass Methanol (second solvent) 47 parts by mass

Into another mixing tank, each of the retardation control agents shown in Table 1, methylene chloride, and methanol were charged (here, total methylene chloride mass / total methanol mass = 87/13; sample Nos. 4A to 11A). In this case, the total methylene chloride mass / total methanol mass was adjusted to 87/13 based on the methylene chloride and methanol contents in the methylene chloride dispersion previously determined by solid content concentration measurement). Each retardation control agent solution / dispersion was prepared by stirring at room temperature. In addition, sample No. shown in Table 1 2A and 3A “untreated smectite” and “untreated mica” are commercially available synthetic smectite fine particles (trade name: Lucentite SPN; manufactured by Corp Chemical), synthetic mica fine particles (trade name: Somasif MPE; Corp) Chemicals) is used as it is.
A dope was prepared by gradually adding and mixing 474 parts by mass of a cellulose acetate solution to 36 parts by mass of the retardation control agent solution and mixing them sufficiently. Each retardation control agent solution / dispersion was prepared so that the amount of the retardation control agent was added as shown in Table 1 with respect to 100 parts by mass of cellulose acetate.

The obtained dope was cast using a band casting machine, and cellulose acetate film No. 1A to 15A (thickness: 80 μm) were produced.
About the manufactured cellulose acetate film, Re (550) value and Rth (550) value at a wavelength of 550 nm, and Re value and Rth value at wavelengths of 630 nm and 450 nm (ΔRe = Re (630) −Re (450), ΔRth = Rth (630) -Rth (450)) value was measured by the method described above. The results are shown in Table 1 below.
In addition, sample No. in Table 1 1 is a cellulose acetate film produced in the same manner except that the retardation control agent solution was not added.
In addition, film No. The addition amount for 4A to 11A is the addition amount of composite particles (smectite particles / mica particles adsorbed with a predetermined organic compound).

From the results in Table 1, in the cellulose acetate film of the examples of the present invention (sample Nos. 4A and 5A), no additive sample No. Compared with 1, the effect of increasing ΔRth, that is, the reverse dispersion of Rth became more remarkable. Comparative Example Cellulose Acetate Film Sample No. 1 in which the same organic compound Q′-8 was added in the same addition amount. In No. 12A, sample No. No additive was added. Compared with 1A, ΔRth hardly changes. Moreover, the cellulose acetate film sample No. of the comparative example which added the unprocessed smectite. Even in 2A, sample No. Compared with 1A, ΔRth hardly changes.
That is, the sample No. of Example of the present invention. In 4A and 5A, by using composite particles in which Q′-8 is adsorbed on smectite or mica, it is not possible to obtain Q′-8 in the film with the same addition amount. It can be understood that optical characteristics with remarkable dispersibility could be achieved.
In addition, in the cellulose acetate film of the examples of the present invention (sample Nos. 6A to 11A), the additive-free sample No. Compared with the comparative example samples (Nos. 13A to 15A) in which one or the same organic compound was added in the same addition amount, a change in which Rth increased and ΔRth decreased was more noticeable. That is, the sample No. of Example of the present invention. In 6A to 11A, by using composite particles in which each organic compound is adsorbed on smectite particles or mica particles, the forward dispersibility cannot be obtained by adding each organic compound to the film in the same addition amount. It can be seen that an optical property of high Rth was achieved.

[Example 2]
(Preparation of composite particles)
Sample No. shown in Table 3 below. As the retardation control agent used for 15B to 28B, exemplary compounds (P-24), (P-28), (Q-17), (Q'-9), (S-8), (U-7) , (V-4) and composite smectite fine particles, composite particles prepared in the same manner as in Example 1 were used.
In addition, the amount of adsorption of the exemplary compounds (P-24), (P-28), (Q-17), and (Q′-9) was quantified by an ultraviolet-visible absorption spectrum and thermal analysis (TG / DTA). However, it was found that the adsorption amount (mass% per total mass of the smectite particles subjected to the adsorption treatment) was as follows.
P-24: 35.9%
P-28: 33.6%
Q-17: 23.8%
Q'-9: 21.4%

Comparative sample No. shown in Table 3 below. As the retardation control agent for 50B and 51B, composite particles prepared by the following method were used.
The inorganic fine particles (rod-like SrCO ₃ , aspect ratio 5) prepared by the method described later and the comparative compound CA-1 were mixed at a ratio of 5 parts by mass with respect to 100 parts by mass of the inorganic fine particles, and 100 parts by volume. Dispersed in methanol and sonicated for 30 minutes. The obtained dispersion was concentrated under reduced pressure to remove the solvent, and composite particles adsorbed with the compound CA-1 were obtained. The presence or absence of adsorption of the compound was confirmed by an ultraviolet-visible absorption spectrum.

The rod-shaped SrCO ₃ fine particles described above were prepared by the following method.
To 1,000 mL (water 600 mL, methanol 400 mL) of a 0.2 mol / L strontium hydroxide suspension as a metal ion source, 600 mL of a 0.1 mol / L ammonium carbonate aqueous solution as a carbonic acid source was stirred and mixed for reaction. It was. The pH in the reaction solution was 12.7.
Next, while stirring the reaction solution, carbon dioxide gas as a carbon dioxide source was supplied in excess from the metal ion source to form a white precipitate in the reaction solution.
In this reaction solution, 0.5 g of 2-ethylhexanoic acid (manufactured by Sigma-Aldrich Japan Co., Ltd.) (hereinafter also referred to as “surface treatment agent 1”) was dissolved in 100 mL of methanol, and then added, for about 30 minutes. Surface treatment was performed by stirring. After sufficiently washing with water, filtration was performed. The obtained precipitate was sufficiently dried and pulverized with an agate mortar to obtain strontium carbonate crystals as anisotropic inorganic particles. The particle size and aspect ratio of the particles were determined from observation results with a transmission electron microscope (TEM). As a result, the particle size was 300 nm and the aspect ratio was 5.

Sample No. shown in Table 1 below. As the retardation control agent for 52B and 53B, composite particles prepared by the following method were used.
To a spherical nano zirconia (ZrO ₂ ) methanol dispersion (10 wt%; manufactured by Sumitomo Osaka Cement Co., Ltd.), the same concentration and amount of the following comparative compound (PA-1) methanol solution was added and stirred for about 1 hour. The precipitate was collected by centrifugation, washed repeatedly with methanol, and then the solvent was distilled off by concentration under reduced pressure to obtain composite particles adsorbed with the compound PA-1. The presence or absence of adsorption of the compound was confirmed by an ultraviolet-visible absorption spectrum.

  In addition, sample No. shown in Table 3 below. In 29B, 30B, 32B, 33B, 35B, 36B, 38B, 39B, 41B, 42B, 44B, 45B, 47B, 48B, the exemplary compounds (P-24), (P-28), (Q-17), ( Q′-9), (S-8), (U-7), and (V-4) were used without being adsorbed on smectite. The amount was the same as the value obtained by multiplying the addition amount of the composite particles of 15B to 28B by the adsorption amount calculated above.

(Production of optically anisotropic film (cellulose acylate film sample No. 11B to 53B))
In the same manner as in Example 1, each of the agents shown in Table 3 was used as a retardation control agent, and for some samples, Example Compound (124) was used as Compound (A), and 100 parts by mass of cellulose acetate. The dope was prepared by mixing with cellulose acetate at the addition amount shown in Table 3. The obtained dope was cast using a band casting machine. A film having a residual solvent amount of 15% by mass was laterally stretched at a stretching ratio of 20% using a tenter under the condition of 165 ° C. to produce a cellulose acetate film (thickness: 80 μm).

  In addition, the absorption wavelength (nm) derived from Mx of the exemplary compound (124) used as the compound (A), the absorption wavelength (nm) derived from My, the angle (°) between My and the molecular major axis, and | My | / | Mx | is shown in Table 2 below.

About each cellulose acetate film produced by the above method, the Re (550) value and Rth (550) value at a wavelength of 550 nm, and the difference between Re value and Rth value at wavelengths of 630 nm and 450 nm (ΔRe = Re (630) −Re (450 ), ΔRth = Rth (630) −Rth (450)) value was measured by the method described above. The results are shown in Table 3 below.
In addition, film sample No. in Table 3 11B is a cellulose acetate film produced in the same manner except that the retardation control agent solution was not added.
In addition, film sample Nos. The addition amount for 15B to 28B and 50B to 53B is the addition amount of composite particles (inorganic particles adsorbed with a predetermined organic compound).

  For comparison, an ultraviolet absorber Ref-1 having no onium cation was adsorbed on the above-mentioned synthetic smectite fine particles, and composite particles were prepared, but adsorbed by UV-visible absorption spectrum and thermal analysis (TG / DTA). When quantitative determination was performed, it was found that there was no adsorption.

However, no. Reference numerals 15B to 18B are reference examples.

From the results in Table 3, the examples of the present invention (Sample Nos. 15B, 17B, 19B, 21B, 23B, 25B, and 27B in Table 3) are compared with the additive-free samples (No. 11B and 12B). It can be understood that the Rth of the film increases and the amount of increase is much larger than the comparative samples (No. 13B, 29B, 32B, 35B, 38B, 41B, 44B, 47B).
Further, in Examples (Sample Nos. 16B, 18B, 20B, 22B, 24B, 26B, and 28B) to which Compound (A) (Exemplary Compound (124)) was added, Exemplified Compounds (P-24) and (P-28) ), (Q-17), (Q′-9), (S-8), (U-7), and (V-4) added without being adsorbed onto the inorganic particles (sample No. 31B, 34B, 37B, 40B, 43B, 46B, 49B), Rth can be increased without impairing the reduction of the reverse dispersion of Re achieved by the exemplary compound (124), that is, the wavelength dispersion of Re. It can be understood that the chromatic dispersion of Rth and Rth can be controlled independently.

On the other hand, when rod-like SrCO ₃ fine particles (sample No. 50B, 51B) and spherical ZrO ₂ fine particles (sample No. 52B, 53B) are used as the non-tabular fine particles, the former induces not only Rth reduction but also Re reduction. Thus, it has been found that independent control of Rth is impossible, and that the Re and Rth cannot be changed at all in the latter case. That is, it can be understood that the above-described effect is exhibited by using tabular grains.

  As described above, the optically anisotropic film of the present invention is useful as an optical film for a liquid crystal display device, particularly as an optical compensation film.

It is drawing which represented typically the state of the organic molecule in the optically anisotropic film of this invention.

Claims (10)

Selected from the group consisting of smectite or mica and compounds represented by the following general formulas (I), (II), (III), and (IV) adsorbed to the smectite or mica by an onium cation. An optically anisotropic film comprising at least one kind of compound molecule and a polymer material.

Wherein A ¹ and A ² each represent a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S— and —CO—; Represents an organic residue necessary for forming a benzo-fused ring or a naphtho-fused ring; R ¹ represents a substituent; m represents an integer of 0 to 4, and R ² and R ³ represent hydrogen, respectively. An atom or Hammett substituent constant σ _p represents an electron withdrawing substituent greater than 0, and R ² and R ³ may combine to form a ring, provided that R, R ¹ , R ² or R ³ has at least one onium cation.)
General formula (II):
Q ⁷¹ -Q ⁷² -OH
(In the general formula (II), Q ⁷¹ is a nitrogen-containing aromatic heterocyclic group, Q ⁷² represents an aromatic ring group. However, Q ⁷¹ or Q ⁷² has at least one substituent containing an onium cation. )

(In the general formula (III), Q ⁸¹ and Q ⁸² each independently represents an aromatic ring group. X ⁸¹ represents NR ⁸¹ (R ⁸¹ represents a hydrogen atom or a substituent), an oxygen atom or a sulfur atom. Q ⁸¹ or Q ⁸² has at least one substituent containing an onium cation.)

(In Formula (IV), Q ⁹¹ and Q ⁹² each represent an aromatic ring group. X ⁹¹ and X ⁹² each represent a hydrogen atom or a substituent, and at least one of them represents a cyano group, a carbonyl group, A sulfonyl group and an aromatic heterocycle, provided that Q ⁹¹ , Q ⁹² , X ⁹¹ or X ⁹² contains at least one onium cation in the substituent. The optically anisotropic film according to claim 1, wherein the aspect ratio of the smectite or mica particles is 5 or more. The optically anisotropic film according to claim 1 or 2, wherein the smectite or mica is synthetic smectite or mica. The optically anisotropic film according to any one of claims 1 to 3, wherein the onium cation is an ammonium cation, a phosphonium cation, an imidazolium cation, or a pyridinium cation. Wherein the polymeric material is optically anisotropic film according to any one of claims 1 to 4, characterized in that a cellulose acylate-based polymer. The optically anisotropic film according to any one of claims 1 to 5, characterized in that it is stretched. Polarizing film, a polarizing plate having a pair of protective films sandwiching the polarizing film, at least one of said protective film, the optically anisotropic film according to any one of claims 1 to 6 A polarizing plate characterized by the above. The liquid crystal display device characterized by having the polarizing plate described in the optically anisotropic layer and / or claim 7 according to claim 1-6. The liquid crystal display device according to claim 8 , wherein the liquid crystal display device is in a VA mode. The molecule of at least one compound selected from the group consisting of the compounds represented by the general formulas (I), (II), (III), and (IV) according to claim 1 is adsorbed by an onium cation. A retardation control agent for polymer films comprising smectite or mica.

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