JP4931539B2 - Optical compensation film, polarizing plate, and liquid crystal display device - Google Patents

Description

  The present invention relates to an optical compensation film, a polarizing plate, and a liquid crystal display device.

The liquid crystal display device has a liquid crystal cell and a polarizing plate. The polarizing plate generally has a protective film and a polarizing film made of cellulose acetate. For example, a polarizing film made of a polyvinyl alcohol film is dyed with iodine, stretched, and both surfaces thereof are laminated with a protective film. Obtained.
In a transmissive liquid crystal display device, polarizing plates are attached to both sides of a liquid crystal cell, and one or more optical compensation films may be disposed.
In a reflective liquid crystal display device, the reflector, liquid crystal cell, one or more optical compensation films, and a polarizing plate are usually arranged in this order.
The liquid crystal cell includes a liquid crystal molecule, two substrates for encapsulating the liquid crystal molecule, and an electrode layer for applying a voltage to the liquid crystal molecule.
The liquid crystal cell performs ON / OFF display depending on the alignment state of the liquid crystal molecules, and can be applied to both transmission and reflection types. ), VA (Vertically Aligned), and ECB (Electrically Controlled Birefringence) have been proposed.

  The optical compensation film is used in various liquid crystal display devices in order to eliminate image coloring and expand the viewing angle. Patent Documents 1 to 8 disclose films having an optically anisotropic layer in which the orientation of the discotic liquid crystal is fixed on a transparent support as the optical compensation film.

  In recent years, with the increasing demand for liquid crystal televisions, further improvement in display quality is desired, and the problem of color misregistration that occurs when viewed obliquely, which has been a major issue, can be achieved by controlling the wavelength dispersion of the optical compensation film. It is clarified by simulation that it can be solved. (Patent Document 9)

  On the other hand, the cellulose acylate film widely used as a transparent support for the transparent protective film and the optical compensation film used on both sides of the polarizing film depends on the humidity of the environment, depending on the acyl group species and the amount of substitution. The absolute values of Re and Rth tend to fluctuate greatly, and it has been pointed out as one of the causes of fluctuations in panel color and viewing angle with respect to humidity changes when applied to liquid crystal display devices, and a solution is desired. ing.

In the techniques described in Patent Documents 1 to 9, no measures have been taken to solve such problems.
Regarding the humidity dependency suppression of cellulose acylate, Patent Document 10 discloses that the humidity change rate of Re by wet drawing (25 ° C., 60% RH to 25 ° C., 10% RH divided by 50) is 2 nm. /% RH or less (Example: ~ 0.1 nm /% RH) is disclosed.
However, since it is essential to adjust the yield stress of the unstretched film in a certain setting region in 90 ° C hot water or 120 ° C steam, the manufacturing process becomes complicated and difficult to control. It is.
Further, Patent Document 11 discloses that by adding an aliphatic polyhydric alcohol ester or the like as a stabilizer, the humidity change rate of Re and Rth (15 to 80% RH based on the value of Re or Rth at 23 ° C. and 55% RH). In other words, a polymer film is disclosed in which the fluctuation range is controlled to be less than 5%.
However, the additive whose effect is specified in the above-mentioned patent document has a high unit price and is not acceptable from the viewpoint of cost as a film.
Further, when 12% by mass was added to cellulose triacetate (degree of acetylation = 60.8%), Rth was 25 ° C. and humidity change (25 ° C., 60% RH to 25 ° C.) in an unstretched film (film thickness = 80 μm). The experiment confirmed that the change at 10% RH was 25 nm, and it was revealed that the effect of improving humidity dependency was insufficient.

  Therefore, a transparent protective film and an optical compensation film for polarizing plates that are sufficiently small in fluctuations in Re and Rth with respect to changes in environmental humidity and have a complicated manufacturing process, and polarizing plates and liquid crystal display devices using the same. It is the present situation that the technological development for obtaining is strongly desired.

Japanese Patent No. 2640083 Japanese Patent No. 2587398 Japanese Patent No. 3118197 International Publication No. 96/37804 Pamphlet International Publication No. 96/31793 Pamphlet JP 11-316378 A Japanese Patent Laid-Open No. 9-21914 JP 2005-37904 A JP 2006-53429 A JP 2003-215337 A JP 2005-106929 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention accurately compensates the liquid crystal cell optically, suppresses color shift depending on the viewing angle direction during high contrast and black display, and changes in Re and Rth with respect to changes in environmental humidity. An object of the present invention is to provide an optical compensation film, a polarizing plate, and a liquid crystal display device that are sufficiently small for polarizing plates.

Means for solving the above problems are as follows. That is,
<1> It contains at least a compound A having a plurality of hydrogen bonding groups in one molecule and a compound B represented by at least one of the following general formulas (I) to (III). It is an optical compensation film.
However, in the following general formula (I), each R ¹² independently represents an aromatic ring or a heterocyclic ring having a substituent in at least one of the ortho position, the meta position, and the para position. Moreover, X < ¹¹ > represents a single bond or -NR < ¹³ >-each independently. Here, each R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Moreover, in the following general formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or a substituent.
In the following general formula (III), Q ⁷¹ represents a nitrogen-containing aromatic heterocycle, and Q ⁷² represents an aromatic ring.
<2> The optical compensation film according to <1>, which satisfies the following formulas (1) to (6).
10 nm <Re (550) <100 nm (1)
100 nm <Rth (550) <200 nm .......... Formula (2)
0.5 ≦ Re (450) / Re (550) ≦ 1.0 (3)
1.0 ≦ Re (630) / Re (550) ≦ 1.5 (4)
1.0 ≦ Rth (450) / Rth (550) ≦ 1.5 (5)
0.5 ≦ Rth (630) / Rth (550) ≦ 1.0 (6)
In the above formulas (1) to (6), Re (λ) is the retardation value of the optical compensation film with respect to light with a wavelength of λnm, and Rth (λ) is the optical compensation with respect to light with a wavelength of λnm. It is the retardation value in the thickness direction of the film.
<3> The optical compensation film according to any one of <1> to <2>, which satisfies the following formula (c) to the following formula (d).
However, in the following formulas (c) to (d), Re (10% RH) is obtained by adjusting the transparent support constituting the optical compensation film until the optical characteristics sufficiently change under the environment of 25 ° C. and 10% humidity. Retation value in the in-plane direction when wetted. Re (80% RH) is a humidity control until the optical properties of the transparent support constituting the optical compensation film change sufficiently at 25 ° C. and 80% humidity. The retardation value in the in-plane direction was Rth (10% RH), and the transparent support constituting the optical compensation film was conditioned until the optical properties sufficiently changed in a 25 ° C., 10% humidity environment. Is the retardation value in the thickness direction, and Rth (80% RH) is the humidity control of the transparent support constituting the optical compensation film until the optical properties change sufficiently in a 10% humidity environment at 25 ° C. When Which is the difference between the direction of the retardation value.
0 nm <Δ (Re (10% RH) −Re (80% RH)) <15 nm Formula (c)
0 nm <Δ (Rth (10% RH) −Rth (80% RH)) <15 nm Formula (d)
<4> The optical compensation film according to any one of <1> to <3>, wherein the compound A contains 1 to 2 aromatic rings as a mother nucleus.
<5> The optical compensation film according to any one of <1> to <4>, wherein the compound A satisfies the following formula (7).
(Number of hydrogen-bonding groups in one molecule / molecular weight of the compound)> 0.01 ... (7)
<6> The optical compensation film according to any one of <1> to <5>, wherein the molecular weight of compound A is 130 or more and 500 or less.
<7> The optical compensation film according to any one of <1> to <6>, wherein the compound B has a ClogP value of 15 or less.
<8> The optical compensation film according to any one of <1> to <7>, comprising cellulose acylate.
<9> The optical compensation film according to <8>, wherein the cellulose acylate satisfies the following formula (8) and formula (9).
2.0 ≦ SA + SB ≦ 3.0 Equation (8)
0 <SB ........... Formula (9)
However, in Formula (8) and Formula (9), SA is the substitution degree of the acetyl group which has substituted the hydrogen atom of the hydroxyl group of a cellulose, and SB has substituted the hydrogen atom of the hydroxyl group of a cellulose. It is the substitution degree of an acyl group having 3 to 22 carbon atoms.
<10> The optical compensation film according to any one of <1> to <9>, wherein a discotic compound layer having a hybrid orientation is formed.
<11> A polarizing plate comprising the optical compensation film according to any one of <1> to <10> on at least one side of a polarizing film.
<12> A liquid crystal display device comprising the liquid crystal cell and the polarizing plate according to <11>.
<13> The liquid crystal display device according to <12>, wherein the liquid crystal cell is an OCB method and a VA method.

  According to the present invention, the liquid crystal cell is accurately optically compensated, the color shift depending on the viewing angle direction at the time of high contrast and black display is suppressed, and the fluctuations of Re and Rth are sufficient with respect to the environmental humidity change. In addition, an optical compensation film for a small polarizing plate, a polarizing plate using the same, and a liquid crystal display device can be obtained.

Hereinafter, the optical compensation film, the polarizing plate, and the liquid crystal display device according to the present invention will be described in detail.
In the description of the present embodiment, “45 °”, “parallel” or “orthogonal” means that the angle is within a range of strictly less than ± 5 °. The error from the exact angle is preferably less than 4 °, more preferably less than 3 °. Regarding the angle, “+” means the clockwise direction, and “−” means the counterclockwise direction. Further, the “slow axis” means a direction in which the refractive index is maximized. The “visible light region” means 380 to 780 nm. Furthermore, the measurement wavelength of the refractive index is a value in the visible light region (λ = 550 nm) unless otherwise specified.

In the description of this embodiment, the term “polarizing plate” is used to mean both a long polarizing plate and a polarizing plate cut into a size incorporated in a liquid crystal device unless otherwise specified. Yes. Here, “cutting” includes “punching” and “cutting out”.
In the description of the present embodiment, “polarizing film” and “polarizing plate” are distinguished from each other. However, “polarizing plate” is a laminate having a transparent protective film that protects the polarizing film on at least one surface of the “polarizing film”. It shall mean the body.

In the description of the present embodiment, the “molecular symmetry axis” refers to a symmetry axis when the molecule has a rotational symmetry axis, but strictly requires that the molecule is rotationally symmetric. is not.
In general, in a discotic liquid crystalline compound, the molecular symmetry axis coincides with an axis perpendicular to the disc surface passing through the center of the disc surface, and in a rod-like liquid crystalline compound, the molecular symmetry axis is the long axis of the molecule. Match.

In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Re (λ) is measured with KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments Co., Ltd.) by making light having a wavelength of λ nm incident in the normal direction of the film.
When the 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 the film surface when Re (λ) is used and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) (if there is no slow axis) Measurement is performed at a total of 6 points by injecting light of wavelength λ nm from each inclined direction in steps of 10 degrees from the normal direction to 50 ° on one side with respect to the film normal direction (with any rotation direction as the rotation axis). Then, KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
The retardation value is measured from two inclined directions with the slow axis as the tilt axis (rotation axis) (if there is no slow axis, the arbitrary direction in the film plane is the rotation axis). Rth can also be calculated from the following formula (A) and formula (B) based on the value, the assumed value of the average refractive index, and the input film thickness value.

・ ・ ・ ・ ・ ・ Formula (A)

Note that Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In the formula (A), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction orthogonal to nx in the plane, and nz is the direction orthogonal to nx and ny. Represents the refractive index.

Rth = ((nx + ny) / 2−nz) × d (Equation (B)

When the 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.
Rth (λ) is from −50 ° to the normal direction of the film, with Re (λ) being the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotary axis). Measured at 11 points by making light of wavelength λ nm incident in 10 ° steps up to + 50 °, and based on the measured retardation value, average refractive index assumption value and input film thickness value. KOBRA 21ADH or WR is calculated.
In the above measurement, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. If the average refractive index is not known, it can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH 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.

(Optical compensation film)
The optical compensation film of the present invention can be used as one side of a transparent protective film of a polarizing plate, but is particularly positively imparted with an optical compensation function (for example, containing additives that express Re and Rth, , Re and Rth are expressed by stretching, and an optically anisotropic layer is further laminated).

<Transparent support>
The transparent support constituting the optical compensation film of the present invention contains a transparent resin material (hereinafter referred to as “transparent resin”), a specific additive (compound A) described later, and a retardation control agent, Other additives may be included as necessary.
The transparent support constituting the optical compensation film of the present invention preferably has a light transmittance of 80% or more.

<< Transparent resin >>
Examples of the transparent resin that forms the transparent support include cellulose acylates. Moreover, optical anisotropy is obtained by extending | stretching the said transparent resin.
Cellulose acylate raw material cellulose used in the present invention includes cotton linter, kenaf, wood pulp (hardwood pulp, conifer pulp), etc., and any cellulose acylate obtained from any raw material cellulose can be used. May be used in combination.
In the present invention, cellulose acylate is produced by esterification from cellulose. However, particularly preferable cellulose is not usable as it is, and linter, kenaf and pulp are purified and used.

In the present invention, cellulose acylate is a fatty acid ester of cellulose. In particular, a lower fatty acid ester of cellulose is more preferable.
Lower fatty acid means a fatty acid having 6 or less carbon atoms. The number of carbon atoms is preferably 2 (cellulose acetate), 3 (cellulose propionate), or 4 (cellulose butyrate).
As the cellulose acylate, cellulose acetate is preferable, and examples thereof include diacetyl cellulose and triacetyl cellulose.
It is also preferable to use a mixed fatty acid ester such as cellulose acetate propionate or cellulose acetate butyrate.

The cellulose acylate used in the present invention preferably has a degree of substitution that satisfies the following formulas (8) to (10) in terms of the degree of substitution of cellulose with hydroxyl groups.
Here, in the following formulas (8) to (10), “SA” represents the substitution degree of the acetyl group substituting the hydrogen atom of the cellulose hydroxyl group, and “SB” represents the hydrogen atom of the cellulose hydroxyl group. Represents the degree of substitution of the acyl group having 3 to 22 carbon atoms which is substituted. “SB” is particularly preferably an acyl group having 3 to 6 carbon atoms.

2.0 ≤ SA + SB ≤ 3.0 ..... Formula (8)
0 <SB ........... Formula (9)
0 ≦ SA <3.0 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Formula (10)

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small.
In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is the same as or higher than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total degree of substitution is preferably substituted with 30% to 40% acyl group, more preferably 31% or more acyl group, and more preferably 32% or more. It is particularly preferable that the substituent is substituted with an acyl group.
In addition to the acetyl group, the hydroxyl group at the 6-position may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms. The degree of substitution at each position can be determined by NMR method or the like.

As the transparent resin used for the transparent support of the present invention, in particular, cellulose triacetate having an acetyl group substitution degree of 2.0 to 3.0, or a total acyl group substitution degree of 2.0 to 2.7, an acetyl group Any of cellulose acetate propionate having a substitution degree of 1.0 to 2.0 and a propionyl group substitution degree of 0.5 to 1.5 is preferable.
Further, the viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
The transparent support preferably has a small polydispersity index (Mw / Mn) measured by gel permeation chromatography (GPC) and a narrow molecular weight distribution.
In addition, Mw shows a mass average molecular weight, Mn shows a number average molecular weight.
The specific value of Mw / Mn is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 1.7. preferable.

<< Compound A >>
The transparent support of the present invention contains an additive (compound A) for reducing fluctuations in Re and Rth with respect to changes in environmental humidity.
The compound A is preferably a compound having at least a plurality of hydrogen bonding groups in one molecule, and the hydrogen bonding group is more preferably selected from a hydroxyl group, an amino group, a thiol group, and a carboxylic acid group, It is particularly preferred to be selected from a hydroxyl group and a carboxylic acid group.
Moreover, it is preferable to have a plurality of different functional groups in one molecule.
Compound A preferably contains 1 to 2 aromatic rings as a mother nucleus, and the value obtained by dividing the number of functional groups contained in one molecule by the molecular weight of the additive is 0.01 or more. It is preferable that
These characteristics are such that the compound A binds (hydrogen bond) to a site where the cellulose acylate resin and water molecules interact (hydrogen bonds), and acts to suppress changes in charge distribution due to desorption of water molecules. However, details are unknown.

  Specific examples of compound A include compounds (A-1) to (A-17) shown below, but are not limited thereto.

Furthermore, it is preferable that the molecular weight of the compound A is 130 or more and 500 or less. When the molecular weight is less than 130, the volatility becomes insufficient, and when it is 500 or more, the solubility in a solvent and the compatibility with the cellulose acylate resin deteriorate.
Specific examples of the compound A satisfying such conditions include the following compounds (A-18) to (A-42), but are not limited thereto.

<Retardation control agent>
In addition to the compound A, the transparent support constituting the optical compensation film of the present invention contains an additive for controlling retardation (hereinafter sometimes referred to as retardation controlling agent).
The retardation control agent preferably has at least one absorption maximum at a wavelength of 250 nm or more, more preferably has at least one absorption maximum at 250 or more and 360 nm or less, and has at least one absorption maximum at 300 or more and 355 nm or less. More preferably, it has.

  The retardation controlling agent is preferably a compound having at least two aromatic rings.

  The retardation controlling agent is preferably selected from compounds represented by the following general formulas (I) to (III).

In the general formula (I), each R ¹² independently represents an aromatic ring or a heterocyclic ring having a substituent in at least one of the ortho position, the meta position, and the para position.
Moreover, X < ¹¹ > represents a single bond or NR < ¹³ >-each independently. Here, each R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

The aromatic ring represented by R ¹² is preferably phenyl or naphthyl, and particularly preferably phenyl. The aromatic ring represented by R ¹² may have at least one substituent at any substitution position. Examples of the substituent include a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxycarbonyl group , Aryloxycarbonyl group, sulfamoyl group, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamide group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio group , An alkenylthio group, an arylthio group, and an acyl group.

The heterocyclic group represented by R ¹² preferably has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, and a heterocycle having the largest number of double bonds is preferred.
The heterocyclic ring 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.
Moreover, the hetero atom of the heterocyclic ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and more preferably a nitrogen atom. As the heterocyclic ring having aromaticity, a pyridine ring (2-pyridyl or 4-pyridyl as the heterocyclic group) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.
When X ¹¹ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is more preferable. The heterocyclic group may have a plurality of nitrogen atoms.
In addition, the heterocyclic group may have a hetero atom other than the nitrogen atom (eg, O, S). Examples of heterocyclic groups having free valences on nitrogen atoms are shown below.

In the general formula ^{(I), X 11} represents a single bond or ^{NR 13} - represents a. R ¹³ independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
The alkyl group represented by R ¹³ may be a cyclic alkyl group or a chain alkyl group, but a chain alkyl group is preferable, and a linear alkyl group is more preferable than a branched chain alkyl group. preferable. The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, particularly preferably 1-8, and 1-6. Is most preferred. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (for example, methoxy group, ethoxy group) and an acyloxy group (for example, acryloyloxy group, methacryloyloxy group).

The alkenyl group represented by R ¹³ may be a cyclic alkenyl group or a chain alkenyl group, but preferably represents a chain alkenyl group, and is a straight chain alkenyl group rather than a branched chain alkenyl group. More preferably it represents a group. The number of carbon atoms in the alkenyl group is preferably 2-30, more preferably 2-20, still more preferably 2-10, particularly preferably 2-8, 2-6 Most preferably. The alkenyl group may have a substituent. Examples of the substituent are the same as those of the alkyl group described above.
The aromatic ring group and heterocyclic group represented by R ¹³ are the same as the aromatic ring and heterocyclic ring represented by R ¹² , and the preferred range is also the same. The aromatic ring group and the heterocyclic group may further have a substituent, and examples of the substituent are the same as those of the aromatic ring and heterocyclic ring of R12.

  Below, the specific example of the retardation control agent represented by general formula (I) used by this invention is shown. Several R shown in the same structural formula in each exemplary compound means the same group. The definition of R is shown after the formula together with the specific example number.

I- (1) phenyl I- (2) 3-ethoxycarbonylphenyl I- (3) 3-butoxyphenyl I- (4) m-biphenylyl I- (5) 3-phenylthiophenyl I- (6) 3- Chlorophenyl I- (7) 3-benzoylphenyl I- (8) 3-acetoxyphenyl I- (9) 3-benzoyloxyphenyl I- (10) 3-phenoxycarbonylphenyl I- (11) 3-methoxyphenyl I- (12) 3-anilinophenyl I- (13) 3-isobutyrylaminophenyl I- (14) 3-phenoxycarbonylaminophenyl I- (15) 3- (3-ethylureido) phenyl I- (16) 3- (3,3-Diethylureido) phenyl I- (17) 3-methylphenyl I- (18) 3-phenoxyphenyl I- (19) 3-hydroxy Eniru

I- (20) 4-ethoxycarbonylphenyl I- (21) 4-butoxyphenyl I- (22) p-biphenylyl I- (23) 4-phenylthiophenyl I- (24) 4-chlorophenyl I- (25) 4-benzoylphenyl I- (26) 4-acetoxyphenyl I- (27) 4-benzoyloxyphenyl I- (28) 4-phenoxycarbonylphenyl I- (29) 4-methoxyphenyl I- (30) 4-ani Linophenyl I- (31) 4-isobutyrylaminophenyl I- (32) 4-phenoxycarbonylaminophenyl I- (33) 4- (3-ethylureido) phenyl I- (34) 4- (3,3 -Diethylureido) phenyl I- (35) 4-methylphenyl I- (36) 4-phenoxyphenyl I- (37) 4-hydroxyl Nil

I- (38) 3,4-diethoxycarbonylphenyl I- (39) 3,4-dibutoxyphenyl I- (40) 3,4-diphenylphenyl I- (41) 3,4-diphenylthiophenyl I- (42) 3,4-dichlorophenyl I- (43) 3,4-dibenzoylphenyl I- (44) 3,4-diacetoxyphenyl I- (45) 3,4-dibenzoyloxyphenyl I- (46) 3,4-diphenoxycarbonylphenyl I- (47) 3,4-dimethoxyphenyl I- (48) 3,4-dianilinophenyl I- (49) 3,4-dimethylphenyl I- (50) 3,4 -Diphenoxyphenyl I- (51) 3,4-dihydroxyphenyl I- (52) 2-naphthyl

I- (53) 3,4,5-triethoxycarbonylphenyl I- (54) 3,4,5-tributoxyphenyl I- (55) 3,4,5-triphenylphenyl I- (56) 3 4,5-triphenylthiophenyl I- (57) 3,4,5-trichlorophenyl I- (58) 3,4,5-tribenzoylphenyl I- (59) 3,4,5-triacetoxyphenyl I -(60) 3,4,5-tribenzoyloxyphenyl I- (61) 3,4,5-triphenoxycarbonylphenyl I- (62) 3,4,5-trimethoxyphenyl I- (63) 3 4,5-trianilinophenyl I- (64) 3,4,5-trimethylphenyl I- (65) 3,4,5-triphenoxyphenyl I- (66) 3,4,5-trihydroxyphenyl

I- (67) phenyl I- (68) 3-ethoxycarbonylphenyl I- (69) 3-butoxyphenyl I- (70) m-biphenylyl I- (71) 3-phenylthiophenyl I- (72) 3- Chlorophenyl I- (73) 3-benzoylphenyl I- (74) 3-acetoxyphenyl I- (75) 3-benzoyloxyphenyl I- (76) 3-phenoxycarbonylphenyl I- (77) 3-methoxyphenyl I- (78) 3-anilinophenyl I- (79) 3-isobutyrylaminophenyl I- (80) 3-phenoxycarbonylaminophenyl I- (81) 3- (3-ethylureido) phenyl I- (82) 3- (3,3-Diethylureido) phenyl I- (83) 3-methylphenyl I- (84) 3-phenoxyphenyl I- (8 ) 3-hydroxyphenyl

I- (86) 4-ethoxycarbonylphenyl I- (87) 4-butoxyphenyl I- (88) p-biphenylyl I- (89) 4-phenylthiophenyl I- (90) 4-chlorophenyl I- (91) 4-benzoylphenyl I- (92) 4-acetoxyphenyl I- (93) 4-benzoyloxyphenyl I- (94) 4-phenoxycarbonylphenyl I- (95) 4-methoxyphenyl I- (96) 4-ani Linophenyl I- (97) 4-isobutyrylaminophenyl I- (98) 4-phenoxycarbonylaminophenyl I- (99) 4- (3-ethylureido) phenyl I- (100) 4- (3,3 -Diethylureido) phenyl I- (101) 4-methylphenyl I- (102) 4-phenoxyphenyl I- (103) 4-hydride Kishifeniru

I- (104) 3,4-diethoxycarbonylphenyl I- (105) 3,4-dibutoxyphenyl I- (106) 3,4-diphenylphenyl I- (107) 3,4-diphenylthiophenyl I- (108) 3,4-dichlorophenyl I- (109) 3,4-dibenzoylphenyl I- (110) 3,4-diacetoxyphenyl I- (111) 3,4-dibenzoyloxyphenyl I- (112) 3,4-diphenoxycarbonylphenyl I- (113) 3,4-dimethoxyphenyl I- (114) 3,4-dianilinophenyl I- (115) 3,4-dimethylphenyl I- (116) 3,4 -Diphenoxyphenyl I- (117) 3,4-dihydroxyphenyl I- (118) 2-naphthyl

I- (119) 3,4,5-triethoxycarbonylphenyl I- (120) 3,4,5-tributoxyphenyl I- (121) 3,4,5-triphenylphenyl I- (122) 3 4,5-triphenylthiophenyl I- (123) 3,4,5-trichlorophenyl I- (124) 3,4,5-tribenzoylphenyl I- (125) 3,4,5-triacetoxyphenyl I -(126) 3,4,5-tribenzoyloxyphenyl I- (127) 3,4,5-triphenoxycarbonylphenyl I- (128) 3,4,5-trimethoxyphenyl I- (129) 3 4,5-trianilinophenyl I- (130) 3,4,5-trimethylphenyl I- (131) 3,4,5-triphenoxyphenyl I- (132) 3,4,5-trihi Rokishifeniru

I- (133) phenyl I- (134) 4-butylphenyl I- (135) 4- (2-methoxy-2-ethoxyethyl) phenyl I- (136) 4- (5-nonenyl) phenyl I- (137 ) P-biphenylyl I- (138) 4-ethoxycarbonylphenyl I- (139) 4-butoxyphenyl I- (140) 4-methylphenyl I- (141) 4-chlorophenyl I- (142) 4-phenylthiophenyl I- (143) 4-Benzoylphenyl I- (144) 4-acetoxyphenyl I- (145) 4-benzoyloxyphenyl I- (146) 4-phenoxycarbonylphenyl I- (147) 4-methoxyphenyl I- ( 148) 4-anilinophenyl I- (149) 4-isobutyrylaminophenyl I- (150) 4-phenoxy Carbonylaminophenyl I- (151) 4- (3-ethylureido) phenyl I- (152) 4- (3,3-diethylureido) phenyl I- (153) 4-phenoxyphenyl I- (154) 4-hydroxy Phenyl

I- (155) 3-Butylphenyl I- (156) 3- (2-methoxy-2-ethoxyethyl) phenyl I- (157) 3- (5-nonenyl) phenyl I- (158) m-biphenylyl I- (159) 3-ethoxycarbonylphenyl I- (160) 3-butoxyphenyl I- (161) 3-methylphenyl I- (162) 3-chlorophenyl I- (163) 3-phenylthiophenyl I- (164) 3 -Benzoylphenyl I- (165) 3-acetoxyphenyl I- (166) 3-benzoyloxyphenyl I- (167) 3-phenoxycarbonylphenyl I- (168) 3-methoxyphenyl I- (169) 3-anilino Phenyl I- (170) 3-isobutyrylaminophenyl I- (171) 3-phenoxycarbonylaminophen Le I- (172) 3- (3- ethylureido) phenyl I- (173) 3- (3,3- diethyl-ureido) phenyl I- (174) 3- phenoxyphenyl I- (175) 3- hydroxyphenyl

I- (176) 2-butylphenyl I- (177) 2- (2-methoxy-2-ethoxyethyl) phenyl I- (178) 2- (5-nonenyl) phenyl I- (179) o-biphenylyl I- (180) 2-ethoxycarbonylphenyl I- (181) 2-butoxyphenyl I- (182) 2-methylphenyl I- (183) 2-chlorophenyl I- (184) 2-phenylthiophenyl I- (185) 2 -Benzoylphenyl I- (186) 2-acetoxyphenyl I- (187) 2-benzoyloxyphenyl I- (188) 2-phenoxycarbonylphenyl I- (189) 2-methoxyphenyl I- (190) 2-anilino Phenyl I- (191) 2-isobutyrylaminophenyl I- (192) 2-phenoxycarbonylaminophen Le I- (193) 2- (3- ethylureido) phenyl I- (194) 2- (3,3- diethyl-ureido) phenyl I- (195) 2-phenoxyphenyl I- (196) 2-hydroxyphenyl

I- (197) 3,4-dibutylphenyl I- (198) 3,4-di (2-methoxy-2-ethoxyethyl) phenyl I- (199) 3,4-diphenylphenyl I- (200) 3 4-diethoxycarbonylphenyl I- (201) 3,4-didodecyloxyphenyl I- (202) 3,4-dimethylphenyl I- (203) 3,4-dichlorophenyl I- (204) 3,4-di Benzoylphenyl I- (205) 3,4-diacetoxyphenyl I- (206) 3,4-dimethoxyphenyl I- (207) 3,4-di-N-methylaminophenyl I- (208) 3,4 Diisobutyrylaminophenyl I- (209) 3,4-diphenoxyphenyl I- (210) 3,4-dihydroxyphenyl

I- (211) 3,5-dibutylphenyl I- (212) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl I- (213) 3,5-diphenylphenyl I- (214) 3 5-diethoxycarbonylphenyl I- (215) 3,5-didodecyloxyphenyl I- (216) 3,5-dimethylphenyl I- (217) 3,5-dichlorophenyl I- (218) 3,5-di Benzoylphenyl I- (219) 3,5-diacetoxyphenyl I- (220) 3,5-dimethoxyphenyl I- (221) 3,5-di-N-methylaminophenyl I- (222) 3,5- Diisobutyrylaminophenyl I- (223) 3,5-diphenoxyphenyl I- (224) 3,5-dihydroxyphenyl

I- (225) 2,4-dibutylphenyl I- (226) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl I- (227) 2,4-diphenylphenyl I- (228) 2, 4-diethoxycarbonylphenyl I- (229) 2,4-didodecyloxyphenyl I- (230) 2,4-dimethylphenyl I- (231) 2,4-dichlorophenyl I- (232) 2,4-di Benzoylphenyl I- (233) 2,4-diacetoxyphenyl I- (234) 2,4-dimethoxyphenyl I- (235) 2,4-di-N-methylaminophenyl I- (236) 2,4- Diisobutyrylaminophenyl I- (237) 2,4-diphenoxyphenyl I- (238) 2,4-dihydroxyphenyl

I- (239) 2,3-dibutylphenyl I- (240) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl I- (241) 2,3-diphenylphenyl I- (242) 2, 3-diethoxycarbonylphenyl I- (243) 2,3-didodecyloxyphenyl I- (244) 2,3-dimethylphenyl I- (245) 2,3-dichlorophenyl I- (246) 2,3-di Benzoylphenyl I- (247) 2,3-diacetoxyphenyl I- (248) 2,3-dimethoxyphenyl I- (249) 2,3-di-N-methylaminophenyl I- (250) 2,3- Diisobutyrylaminophenyl I- (251) 2,3-diphenoxyphenyl I- (252) 2,3-dihydroxyphenyl

I- (253) 2,6-dibutylphenyl I- (254) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl I- (255) 2,6-diphenylphenyl I- (256) 2, 6-diethoxycarbonylphenyl I- (257) 2,6-didodecyloxyphenyl I- (258) 2,6-dimethylphenyl I- (259) 2,6-dichlorophenyl I- (260) 2,6-di Benzoylphenyl I- (261) 2,6-diacetoxyphenyl I- (262) 2,6-dimethoxyphenyl I- (263) 2,6-di-N-methylaminophenyl I- (264) 2,6- Diisobutyrylaminophenyl I- (265) 2,6-diphenoxyphenyl I- (266) 2,6-dihydroxyphenyl

I- (267) 3,4,5-tributylphenyl I- (268) 3,4,5-tri (2-methoxy-2-ethoxyethyl) phenyl I- (269) 3,4,5-triphenylphenyl I- (270) 3,4,5-triethoxycarbonylphenyl I- (271) 3,4,5-tridodecyloxyphenyl I- (272) 3,4,5-trimethylphenyl I- (273) 3 4,5-trichlorophenyl I- (274) 3,4,5-tribenzoylphenyl I- (275) 3,4,5-triacetoxyphenyl I- (276) 3,4,5-trimethoxyphenyl I- (277) 3,4,5-Tri-N-methylaminophenyl I- (278) 3,4,5-triisobutyrylaminophenyl I- (279) 3,4,5-triphenoxyphenyl I- 280) 3,4,5-hydroxyphenyl

I- (281) 2,4,6-tributylphenyl I- (282) 2,4,6-tri (2-methoxy-2-ethoxyethyl) phenyl I- (283) 2,4,6-triphenylphenyl I- (284) 2,4,6-triethoxycarbonylphenyl I- (285) 2,4,6-tridodecyloxyphenyl I- (286) 2,4,6-trimethylphenyl I- (287) 2, 4,6-trichlorophenyl I- (288) 2,4,6-tribenzoylphenyl I- (289) 2,4,6-triacetoxyphenyl I- (290) 2,4,6-trimethoxyphenyl I- (291) 2,4,6-Tri-N-methylaminophenyl I- (292) 2,4,6-triisobutyrylaminophenyl I- (293) 2,4,6-triphenoxyphenyl I- 294) 2,4,6-hydroxyphenyl

I- (295) pentafluorophenyl I- (296) pentachlorophenyl I- (297) pentamethoxyphenyl I- (298) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl I- (299) 5 -N-methylsulfamoyl-2-naphthyl I- (300) 6-N-phenylsulfamoyl-2-naphthyl I- (301) 5-ethoxy-7-N-methylsulfamoyl-2-naphthyl I -(302) 3-methoxy-2-naphthyl I- (303) 1-ethoxy-2-naphthyl I- (304) 6-N-phenylsulfamoyl-8-methoxy-2-naphthyl I- (305) 5 -Methoxy-7-N-phenylsulfamoyl-2-naphthyl I- (306) 1- (4-methylphenyl) -2-naphthyl I- (307) 6,8-di-N Methylsulfamoyl-2-naphthyl I- (308) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl I- (309) 5-acetoxy-7-N-phenylsulfamoyl- 2-Naphtyl I- (310) 3-benzoyloxy-2-naphthyl

I- (311) 5-acetylamino-1-naphthyl I- (312) 2-methoxy-1-naphthyl I- (313) 4-phenoxy-1-naphthyl I- (314) 5-N-methylsulfamoyl -1-Naphtyl I- (315) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl I- (316) 5-methoxy-6-N-ethylsulfamoyl-1-naphthyl I- (317) 7 -Tetradecyloxy-1-naphthyl I- (318) 4- (4-methylphenoxy) -1-naphthyl I- (319) 6-N-methylsulfamoyl-1-naphthyl I- (320) 3-N , N-dimethylcarbamoyl-4-methoxy-1-naphthyl I- (321) 5-methoxy-6-N-benzylsulfamoyl-1-naphthyl I- (322) 3,6-di-N-fe Rusurufamoiru-1-naphthyl

I- (323) methyl I- (324) ethyl I- (325) butyl I- (326) octyl I- (327) dodecyl I- (328) 2-butoxy-2-ethoxyethyl I- (329) benzyl I -(330) 4-methoxybenzyl

I- (331) methyl I- (332) phenyl I- (333) butyl

  Below, the compound represented by general formula (II) is demonstrated.

In the general formula (II), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a hydrogen atom or a substituent.
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are each represented by an alkyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, in particular, Preferably it is a C1-C20 alkyl group, for example, methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group , A cyclohexyl group, etc.), an alkenyl group (preferably an alkenyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, such as a vinyl group or an allyl group. , 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably carbon An alkynyl group having 2 to 20 carbon atoms, such as a propargyl group and a 3-pentynyl group, and an aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, and particularly preferably having a carbon number). 6-12 aryl groups, including, for example, phenyl group, p-methylphenyl group, naphthyl group, etc., substituted or unsubstituted amino group (preferably having 0 to 40 carbon atoms, more preferably 0 carbon atoms). To 30 and particularly preferably an amino group having 0 to 20 carbon atoms, and examples thereof include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and an anilino group.

  In addition, as the substituent, an alkoxy group (preferably an alkoxy group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, and a butoxy group. Group), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, such as a phenyloxy group, 2 -A naphthyloxy group etc. are mentioned), an acyl group (preferably C1-C40, more preferably C1-C30, especially preferably C1-C20 acyl group, for example, acetyl group, benzoyl Group, formyl group, pivaloyl group, etc.), alkoxycarbonyl group (preferably having 2 to 40 carbon atoms, more preferably 2 to 3 carbon atoms). And particularly preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group, and an aryloxycarbonyl group (preferably having 7 to 40 carbon atoms, more preferably having 7 carbon atoms). To 30 and particularly preferably an aryloxycarbonyl group having 7 to 20 carbon atoms, such as a phenyloxycarbonyl group, and an acyloxy group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms). And particularly preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetoxy group and a benzoyloxy group).

  As the substituent, an acylamino group (preferably an acylamino group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, and particularly preferably 2 to 20 carbon atoms, such as an acetylamino group, a benzoylamino group, and the like. Etc.), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, such as a methoxycarbonylamino group An aryloxycarbonylamino group (preferably 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, particularly preferably 7 to 20 carbon atoms, such as phenyloxy A carbonylamino group), a sulfonylamino group (preferably A sulfonylamino group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group), a sulfamoyl group ( A sulfamoyl group having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, and particularly preferably 0 to 20 carbon atoms is preferable, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group. And a carbamoyl group (preferably a carbamoyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, such as an unsubstituted carbamoyl group). Methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group, etc. Is) is included.

In addition, as the substituent, an alkylthio group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a phenylthio group), a sulfonyl group (Preferably a sulfonyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, and examples thereof include a mesyl group and a tosyl group), a sulfinyl group (preferably A sulfinyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a methanesulfinyl group and a benzenesulfinyl group, and a ureido group (preferably carbon A ureido group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms. Ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 40 carbon atoms, more preferably having 1 to 30 carbon atoms, and particularly preferably having 1 to 20 carbon atoms) Group such as diethyl phosphoramide group and phenylphosphoric acid amide group), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group Group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, such as a nitrogen atom A heterocyclic group having a heteroatom such as oxygen atom, sulfur atom, etc., for example, an imidazolyl group, a pyridyl group, a quinolyl group Furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, 1,3,5-triazyl group and the like, silyl group (preferably having 3 to 40 carbon atoms, more preferably Is a silyl group having 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group.
These substituents may be further substituted with these substituents. Further, when two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.

Examples of the substituent represented by each of R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ include an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, or a halogen Atoms are preferred.

  Although the specific example of a compound represented by general formula (II) below is given, it is not limited to these.

The compound represented by general formula (III) is demonstrated below.
In the general formula (III), Q ⁷¹ represents a nitrogen-containing aromatic heterocycle, and Q ⁷² represents an aromatic ring.
In the general formula (III), Q ⁷¹ represents a nitrogen-containing aromatic heterocycle, preferably a 5- to 7-membered nitrogen-containing aromatic heterocycle, and a 5- to 6-membered nitrogen-containing aromatic heterocycle is More preferred.

  Examples of the nitrogen-containing aromatic heterocycle include imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzotriazole, benzothiazole, benzoxazole, benzoselenazole, thiadiazole, oxadiazole, naphthothiazole, naphthoxazole, Each ring such as azabenzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, triazaindene, tetrazaindene and the like is preferable, triazine and a 5-membered nitrogen-containing aromatic heterocycle are more preferable, specifically 1,3,5-triazine, imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, benzotriazole, benzothiazole, benzoxazole, thiadia Lumpur, each ring are preferred, such as oxadiazole, 1,3,5-triazine ring and a benzotriazole ring is particularly preferred.

Nitrogen-containing aromatic heterocyclic ring represented by Q ⁷¹ may have a substituent, the substituent may be the substituent 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. Aromatic ring represented by Q ⁷² 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 (for example, a benzene ring or a naphthalene ring), and an aromatic carbon ring having 6 to 20 carbon atoms. A hydrogen ring is more preferable, an aromatic hydrocarbon ring having 6 to 12 carbon atoms is further preferable, and a benzene ring is particularly preferable.

  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. As the aromatic heterocycle, pyridine, triazine, and quinoline are preferable.

The aromatic ring represented by Q ^72, an aromatic hydrocarbon ring is preferably a naphthalene ring, more preferably a benzene ring, a benzene ring is particularly preferred. Q ⁷² may further have a substituent, and the following substituent T is preferred.
Examples of the substituent T include alkyl groups (preferably those having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and t-butyl. Group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc., alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8, for example, vinyl group, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms). Yes, for example, propargyl group, 3-pentynyl group, etc., aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 and particularly preferably 6 to 1). For example, 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, etc.), an alkoxy group (preferably having a carbon number of 1-20, more preferably 1-12, particularly preferably 1-8, for example, a methoxy group, an ethoxy group, a butoxy group. Etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms such as phenyloxy group and 2-naphthyloxy group), acyl group (preferably carbon The number is 1 to 20, more preferably 1 to 16, and particularly preferably 1 to 12. For example, acetyl group, benzoyl group, formyl group, A valoyl group), an alkoxycarbonyl group (preferably having a carbon number of 2-20, more preferably 2-16, particularly preferably 2-12, such as a methoxycarbonyl group, an ethoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably Has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as a phenyloxycarbonyl group, an acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly Preferably it is 2-10, for example, an acetoxy group, a benzoyloxy group, etc.) etc. are mentioned.

  Other examples of the substituent T include an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and 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 carbon atoms, particularly preferably 2 to 12 carbon atoms such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms). , More preferably 7 to 16, particularly preferably 7 to 12, for example, phenyloxycarbonylamino group, etc., sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 1). 12 such as methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamo Ru group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms such as sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.) A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group), an alkylthio group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group, and an arylthio group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, Particularly preferred are 6 to 12, for example, phenylthio group and the like, and sulfonyl group (preferably Or 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a mesyl group and a tosyl group.), A sulfinyl group (preferably 1 to 20 carbon atoms, more preferably Is 1 to 16, 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 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, ureido group, methylureido group, phenylureido group, etc.), 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. , Phenyl phosphoric acid amide, etc.).

  Furthermore, as the substituent T, other than that, hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid Group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having a carbon number of 1-30, more preferably 1-12, and examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically Is, for example, imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably Is 3 to 30, particularly preferably 3 to 24, such as trimethylsilyl group and triphenylsilyl group. ), And the like.

  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.

  Specific examples of the compound represented by the general formula (III) are listed below, but the present invention is not limited to the following specific examples.

  The retardation control agent used in the present invention is preferably a compound represented by general formula (I) or general formula (II), and more preferably a compound represented by general formula (II). Moreover, it is also preferable to mix the compound represented by general formula (III) with the compound represented by general formula (I) and (II).

  The addition amount of the retardation control agent (compounds represented by the general formulas (I) to (III)) used in the present invention is preferably 0.1 to 30% by mass with respect to the base polymer of the film. 5 to 20% by mass is more preferable, and 1 to 10% by mass is even more preferable. When using 2 or more types, it is preferable that the total amount satisfy | fills the range of the said addition amount.

  The retardation controlling agent used in the present invention preferably exhibits liquid crystallinity. It is more preferable to exhibit liquid crystallinity (having thermotropic liquid crystallinity) by heating, and it is preferable to exhibit liquid crystallinity in a temperature range of 100 to 300 ° C. The liquid crystal phase is preferably a columnar phase, a nematic phase, or a smectic phase, and more preferably a columnar phase.

[ClogP value]
In addition, the retardation control agent used in the present invention preferably has a ClogP value of 15 or less, more preferably 12 or less.

Here, the LogP value is an index representing the degree of hydrophobicity of a substance, and is, for example, a value represented by a measured octanol / water partition coefficient.
As a method of calculating the LogP value (log _{Po / w} value), “Solubility of the organic compound in n-octanol at 25 ° C.” is set to So, and “Solubility of the organic compound in pure water at 25 ° C.” Is represented by logP = So / Sw.
Although these can be measured using n-octanol and water as described above, in the present invention, a logP value estimation program (CLOGP program incorporated in PC Models of Daylight Chemical Information Systems) is used. Thus, the distribution coefficient (ClogP value) can be obtained.

The log P value was estimated to be an index for determining whether or not the retardation control agent coexists with the compound A in the polymer.
Since compound A has a plurality of hydrogen bonding groups in one molecule, it has a high hydrophilicity and tends to exhibit a small log P value with respect to the retardation control agent of the present invention.
Therefore, the present inventors have found that the retardation control agent having a log P value of 15 or more has high hydrophobicity and bleeds out (whitens) during film formation.

  The retardation control agent may be added simultaneously with the dissolution of the base polymer of the film, or may be added to the dope after dissolution. In particular, a mode in which a UV absorber solution is added to the dope immediately before casting using a static mixer or the like is preferable because the spectral absorption characteristics can be easily adjusted.

  In the retardation controlling agent, the compound A may have retardation developing ability. In this case, it is preferable to adjust the addition amount of both. That is, since the compound A added for improving the humidity dependency expresses different retardations depending on the structure, the structure and amount of the retardation control agent are required to provide appropriate retardation as an optical compensation film. Need to be adjusted.

<Plasticizer>
A conventionally known plasticizer may be added to the transparent support in order to improve the mechanical properties as a film or to increase the drying speed.
Examples of the plasticizer include phosphate esters, carboxylic acid esters, and the like. For example, p. 16 and the like.
Examples of the carboxylic acid constituting the carboxylic acid esters include aliphatic carboxylic acids, oxycarboxylic acids (such as citric acid and malic acid), and aromatic carboxylic acids (such as phthalic acid).
As other compounds applied to the plasticizer, esterified compounds of alkane polyols and carboxylic acids described in JP-A Nos. 11-124445 and 2001-247717 are also preferable.
The addition amount of the plasticizer is preferably 0.05 to 25% by mass and more preferably 1 to 20% by mass with respect to 100 parts by mass of the cellulose acylate.
Moreover, when the effect of an additive is reduced by the combined use with the compound A, it is preferable to adjust by reducing the addition amount of a plasticizer. In many cases, the compound A has a plasticizer function, and it is not always necessary to add a plasticizer separately from the compound A.

<< Fine particle >>
In the present invention, it is preferable to add fine particles to the cellulose acylate composition (transparent support) in order to maintain good curl suppression, transportability, and scratch resistance of the film.
The fine particles to be added are not particularly limited as long as the materials exhibit the above-described functions, and those having a Mohs hardness of 2 to 10 are preferable.

  As the fine particles, either an inorganic compound or an organic compound may be used. Preferred specific examples of the fine particles of the inorganic compound include compounds containing silicon, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, barium oxide, and oxidation. Zirconium, strontium oxide, antimony oxide, tin oxide, tin oxide / antimony, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, etc. Among these, an inorganic compound containing silicon and zirconium oxide are more preferable, and silicon dioxide is more preferable because turbidity of the transparent support can be reduced.

It is also preferable to employ surface-treated inorganic fine particles as the fine particles of the inorganic compound to be added because dispersibility in cellulose acylate is good.
Examples of the surface treatment method for the fine particles of the inorganic compound include a method described in JP-A No. 54-57562. Examples of the inorganic compound fine particles include inorganic compound fine particles described in JP-A No. 2001-151936.

  Specific examples of the fine particles of the organic compound include polymers such as crosslinked polystyrene, silicone resin, fluororesin, and acrylic resin. Among these, silicone resins are more preferable, and among the silicone resins, a three-dimensional network structure is used. Particularly preferred are silicone resins having

The primary average particle size (hereinafter also referred to as particle size) of the fine particles is preferably 0.001 to 1 μm, more preferably 0.005 to 0.4 μm, and still more preferably 0.005 to 0.1 μm. If it is these ranges, haze can be suppressed low and the unevenness | corrugation of the film surface after film forming can be made small, without impairing the mechanical physical property as a film.
The amount of fine particles added to cellulose acylate is preferably 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.2 parts by mass with respect to 100 parts by mass of cellulose acylate.

<< Other additives >>
The transparent support of the present invention may further contain an ultraviolet inhibitor, a deterioration inhibitor, a release agent, an antistatic agent, and the like.
Examples of the ultraviolet light inhibitor include hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, and cyanoacrylate compounds.
Examples of the deterioration preventing agent include antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, and light stabilizers such as hindered amines.
Details of these ultraviolet light inhibitor, deterioration preventive agent, release agent, antistatic agent and the like are described in p. The materials described in detail in 17-22 are preferably used.

<Method for producing transparent support>
As a manufacturing method of the transparent support body in this invention, it is preferable to manufacture a cellulose acylate film by a solvent cast method, and a film is manufactured using the solution (dope) which melt | dissolved the cellulose acylate in the organic solvent.
As an organic solvent used for the said manufacturing method, a conventionally well-known organic solvent is mentioned, For example, the thing of the range of 17-22 in a solubility parameter (Solubility Parameter) is preferable.
Here, the solubility parameter δ can be calculated by the following formula (x).
δ = (E / V) ^1/2 Equation (x)
In the above formula (x), E represents cohesive energy (molar evaporation energy), and V represents molecular volume (molar volume).
For the solubility parameter, see, for example, J. Org. Brandrup, E.I. “Polymer Handbook (4th edition), VII / 671-VII / 714”.

Examples of such organic solvents include lower aliphatic hydrocarbon chlorides, lower aliphatic alcohols, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and those having 3 to 12 carbon atoms. Examples include ethers, aliphatic hydrocarbons having 5 to 8 carbon atoms, and aromatic hydrocarbons having 6 to 12 carbon atoms.
In addition, ether, ketone, and ester may have a cyclic structure.
A compound having two or more functional groups of ether, ketone, and ester (that is, —O—, —CO—, and COO—) can also be used as the organic solvent.
The organic solvent may have another functional group such as an alcoholic hydroxyl group.
In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.
Specifically, for example, p. Examples thereof include compounds described in detail in 12 to 16.

In particular, in the present invention, the solvent is preferably used by mixing two or more kinds of organic solvents, and particularly preferably three or more kinds of mixed solvents different from each other.
As the three or more kinds of mixed solvents different from each other, the first solvent is a ketone having 3 to 4 carbon atoms and an ester having 3 to 4 carbon atoms or a mixture thereof, and the second solvent Is selected from ketones having 5 to 7 carbon atoms, or acetoacetate, and the third solvent is selected from alcohol having a boiling point of 30 to 170 ° C. or hydrocarbon having a boiling point of 30 to 170 ° C. Is preferred.
In particular, it is preferable from the viewpoint of the solubility of cellulose acylate to use 20 to 90% by mass of acetate, 5 to 60% by mass of ketones, and 5 to 30% by mass of alcohols.
Further, non-halogen organic solvent systems that do not contain halogenated hydrocarbons are particularly preferred.
Technically, halogenated hydrocarbons such as methylene chloride can be used without problems, but from the viewpoint of the global environment and working environment, it is preferable that the organic solvent is substantially free of halogenated hydrocarbons.
Here, “substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass). Further, it is preferable that no halogenated hydrocarbon such as methylene chloride is detected at all from the produced transparent support.

Specific examples of the organic solvent used in the present invention include paragraph numbers [0021] to [0025] in JP-A No. 2002-146043 and paragraph numbers [0016] to [0021] in JP-A No. 2002-146045. ] Examples of the organic solvent described in the above.
In addition to the organic solvent of the present invention, the dope used in the present invention may contain fluoroalcohol and methylene chloride in an amount of 10% by mass or less, more preferably 5% by mass or less of the total organic solvent amount of the present invention. It is preferable for improving the transparency of the film and for increasing the solubility.
Examples of the fluoroalcohol include compounds described in paragraph No. [0020] of JP-A-8-143709, paragraph No. [0037] of JP-A-11-60807, and the like. These fluoroalcohols may be used alone or in combination.
When preparing the cellulose acylate solution of the present invention, the container may be filled with an inert gas such as nitrogen gas.
Further, the viscosity of the cellulose acylate solution immediately before film formation may be within a range where casting can be performed, and is usually adjusted to a range of 10 to 2,000 ps · s, preferably 30 to 400 ps. -S is more preferable.

Regarding the preparation of the cellulose acylate solution (dope) of the present invention, the dissolution method is not particularly limited, and may be a room temperature dissolution method, a cooling dissolution method, a high temperature dissolution method, or a combination thereof.
Regarding these dissolution methods, for example, JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544, JP-A-10-95854, JP-A-10-45950 JP, 2000-53784, JP 11-322946, JP 11-322947, JP 2-276830, JP 2000-273239, JP 11-71463, JP 04-259511. , JP-A 2000-273184, JP-A 11-323017, JP-A 11-302388, and the like.
Moreover, these techniques can be appropriately applied to the method for dissolving these cellulose acylates in the organic solvent within the scope of the present invention.
Further, the dope solution of cellulose acylate is usually concentrated and filtered, and is similarly described in detail in the above-mentioned JIII Journal of Technical Disclosure No. 01-1745. In addition, when it melt | dissolves at high temperature, it is the case where it is more than the boiling point of the organic solvent to be used, and in that case, it uses in a pressurized state.

Next, in the present invention, a method for producing a transparent support using a cellulose acylate solution will be described.
As a method and equipment for producing a transparent support, a conventionally known solution casting film forming method and solution casting film forming apparatus called a drum method or a band method used for producing a transparent support are used.
Here, the film forming process will be described by taking the band method as an example. A dope (cellulose acylate solution) prepared from a dissolving machine (kettle) is temporarily stored in a storage kettle, and bubbles contained in the dope are removed. Foam the final preparation.
Next, it is important to remove foreign matters from the prepared dope by microfiltration. Specifically, it is preferable to use a filter having a pore size as small as possible as long as the components in the dope solution are not removed.
For filtration, a filter having an absolute filtration accuracy of 0.1 to 100 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 25 μm is preferably used.
Here, the thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, it is preferable to perform filtration at a filtration pressure of 1.47 MPa or less, more preferably filtration at a filtration pressure of 0.98 MPa or less, and further preferably filtration at a filtration pressure of 0.20 MPa or less.

Moreover, in order to perform microfiltration, it is also preferable to perform filtration several times with the pore diameter of the filter being sequentially reduced.
The type of filter medium for performing microfiltration is not particularly limited as long as it has the above performance, and examples thereof include a filament type, a felt type, and a mesh type.
The material of the filter medium for finely filtering the dispersion is not particularly limited as long as it has the above performance and does not adversely affect the coating solution, and examples thereof include stainless steel, polyethylene, polypropylene, and nylon.

The prepared dope is fed from the dope discharge port to the pressure die through a pressure metering gear pump that can deliver the metered liquid with high accuracy, for example, by the number of rotations, 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 a peeling point where the metal support is uniformly cast on the metal support of the extended portion and the metal support has substantially gone around.
Both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width, dried, then transported by a roll group of a drying device, dried, and wound to a predetermined length by a winder. take. The combination of the tenter and the roll group drying apparatus varies depending on the purpose.
For each of these production steps (casting (including co-casting), metal support, drying, peeling, stretching, etc.), p. The content described in detail in 25-30 is mentioned.
In the casting step, one type of cellulose acylate solution may be cast as a single layer, or two or more types of cellulose acylate solutions may be cast simultaneously and / or sequentially.

Next, a preferred stretching method for the present invention will be specifically described.
The cellulose acylate film of the present invention is preferably stretched in the width direction when applied to a polarizing plate. About this stretching method, for example, in JP-A-62-115035, JP-A-4-152125, JP-A-4-284221, JP-A-4-298310, JP-A-11-48271, etc. Are listed.
In addition, as described above, the cellulose acylate film of the present invention is stretched under the conditions of 100 to 250 ° C., which is Tg−50 ° C. of the film to Tg + 100 ° C. of the film.
The cellulose acylate film of the present invention may be stretched uniaxially or biaxially. Further, it may include a stretching step and a shrinking step for shrinking depending on the purpose.
Moreover, the cellulose acylate film of the present invention can be stretched by a treatment during drying, and is particularly effective when a solvent remains. For example, the cellulose acylate film is stretched by adjusting the speed of the conveyance roller of the cellulose acylate film so that the take-up speed of the cellulose acylate film is higher than the peeling speed of the cellulose acylate film.
The cellulose acylate film can also be stretched by conveying the cellulose acylate film while holding it with a tenter and gradually widening the width of the tenter.
Furthermore, after the cellulose acylate film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).
The stretch ratio of the cellulose acylate film of the present invention (ratio of increase due to stretching relative to the original length) is preferably 0.5 to 300%, more preferably 1 to 200%, and more preferably 1 to 100%. % Stretching is more preferred.

The cellulose acylate film of the present invention is preferably produced by sequentially or continuously performing a film-forming process by a solvent cast method and a stretching process for stretching the film formed, and the stretching ratio is 1.2. It is preferable that it is not less than twice and not more than 1.8 times.
Moreover, the said extending process may be performed by 1 step | paragraph and may be performed by multiple steps | paragraphs. When it is performed in multiple stages, the product of the stretching ratios may be in the above range (1.2 times or more and 1.8 times or less).

The stretching speed is preferably 5 to 1,000% / min, and more preferably 10 to 500% / min.
Furthermore, it is preferable to perform the said extending | stretching process with a heat roll and / or a radiant heat source (IR heater etc.), and warm air. Moreover, you may provide a thermostat in order to improve the uniformity of temperature.
When performing uniaxial stretching by roll stretching, it is preferable that L / W which is a ratio of the distance (L) between rolls and the film width (W) of a protective film is 2.0-5.0.

Furthermore, it is preferable to provide a preheating step before the stretching step, and heat treatment may be performed after the stretching step. The heat treatment temperature is preferably a temperature between 50 ° C. lower than the glass transition temperature (Tg) of the cellulose acetate film and 100 ° C. higher than the glass transition temperature (Tg). It is preferably 3 minutes.
Moreover, the heating method may be zone heating or partial heating using an infrared heater, and may slit both ends of the cellulose acetate film during or at the end of the heating step. And it is preferable to collect | recover and reuse as a raw material the slit waste produced at this time.

  Regarding the tenter, in Japanese Patent Application Laid-Open No. 11-077718, when the web is dried while maintaining the width with the tenter, the blowing method, the blowing angle, the wind speed distribution, the wind speed, the air volume, the temperature difference, the air volume difference, and the upper and lower air blowing are performed. By appropriately controlling the use of air volume ratio and high specific heat drying gas, etc., it is possible to ensure quality prevention such as flatness when increasing the speed by the solution casting method or widening the web width. These techniques may be employed in the present invention.

  Japanese Patent Application Laid-Open No. 11-077782 describes a technique in which a stretched thermoplastic resin film is heat treated by providing a temperature gradient in the width direction of the film in the thermal relaxation process after the stretching process in order to prevent unevenness. This technique may be employed in the heat treatment step.

  Japanese Patent Laid-Open No. 4-204503 describes a technique for stretching the film so that the solvent content of the film is 2 to 10% based on the solid content in order to prevent the occurrence of unevenness, and this technique is employed in the present invention. May be.

  Japanese Patent Application Laid-Open No. 2002-248680 discloses that tenter clip biting width D ≦ (33 / (log stretch ratio × log volatile content)) in order to suppress curling due to the regulation of clip biting width. Describes a technique for suppressing curling and facilitating film conveyance after the stretching process, and this technique may be employed in the present invention.

  Japanese Patent Application Laid-Open No. 2002-337224 describes a technique for switching the tenter conveyance to the first half pin and the second half clip in order to achieve both high-speed soft film conveyance and stretching, and this technique is employed in the present invention. May be.

Japanese Patent Application Laid-Open No. 2002-187960 discloses that a cellulose ester dope solution is cast on a casting support for the purpose of easily improving the viewing angle characteristics and improving the viewing angle. The web (film) peeled off from the support for stretching is 1.0 to 4.0 times in at least one direction while the amount of residual solvent in the web is in the range of 100% by mass or less, particularly 10 to 100% by mass. An invention having optically biaxiality obtained by stretching is described.
As a further preferred embodiment of this technique, it is also described that the film is stretched by 1.0 to 4.0 times in at least one direction while the residual solvent amount in the web is in the range of 100% by mass or less, particularly 10 to 100% by mass. Has been.
In addition, as another stretching method of this technique, a difference in circumferential speed is applied to a plurality of rolls, and the roll is stretched in the longitudinal direction using the difference in circumferential speed between the rolls, and both ends of the web are fixed with clips or pins. A method of extending the gap between the pins in the direction of travel and extending in the vertical direction, a method of extending the width in the horizontal direction and extending in the horizontal direction, a method of extending the length and width simultaneously and extending in both the vertical and horizontal directions, a method of combining these, etc. Are also listed.
Furthermore, in the case of the so-called tenter method, it has been shown that driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced. You may employ | adopt for invention.

JP-A-2003-014933 discloses that an additive and a resin are added in order to produce an optical compensation film having little additive bleed-out, no delamination phenomenon between layers, and good slipperiness and excellent transparency. A dope A containing an additive and an organic solvent, and a dope B containing no additive or a resin having a lower additive content than the dope A, an additive and an organic solvent, and the dope A being a core layer Then, after co-casting on the support so that the dope B becomes a surface layer and evaporating the organic solvent until it can be peeled, the web is peeled off from the transparent support, and further in the resin film during stretching A technique is described in which the residual solvent is stretched 1.1 to 1.3 times in at least a uniaxial direction in the range of 3 to 50% by mass.
As a further preferred embodiment of this technique, the web is peeled from the support, and further stretched at least uniaxially in the uniaxial direction at a stretching temperature of 140 to 200 ° C., and a resin and an organic solvent are included. Dope A, dope B containing resin, fine particles, and organic solvent is prepared, until the dope A becomes a core layer and the dope B becomes a surface layer, and is co-cast on a transparent support until it becomes peelable. After evaporating the organic solvent, the web is peeled from the support, and further stretched 1.1 to 3.0 times in the uniaxial direction in the range of 3 to 50% by mass of the residual solvent in the resin film during stretching. Furthermore, the film is stretched 1.1 to 3.0 times at least in a uniaxial direction at a stretching temperature of 140 to 200 ° C., a dope A containing a resin, an organic solvent and an additive, and an additive or no additive. Resin with less content than Dope A A dope B containing an additive and an organic solvent, and a dope C containing a resin, fine particles, and an organic solvent are prepared. The dope A is a core layer, the dope B is a surface layer, and the dope C is a surface opposite to the dope B. After co-casting on the support so as to form a layer and evaporating the organic solvent until it can be peeled, the web is peeled from the support, and the amount of residual solvent in the resin film during stretching is 3 to 3 Stretching at least uniaxially 1.1 to 3.0 times in the range of 50% by mass, stretching at least uniaxially 1.1 to 3.0 times in the range of the stretching temperature of 140 to 200 ° C., Dope A The additive amount in the resin is 1 to 30% by mass with respect to the resin, the additive amount in the dope B is 0 to 5% by mass with respect to the resin, and the additive is a plasticizer, an ultraviolet absorber, or a retardation. Being a control agent, existence in dope A and dope B The solvent is described to be preferable to use that it contains methylene chloride, or 50 wt% methyl acetate with respect to the total organic solvents may be employed these techniques to the present invention.

Japanese Patent Application Laid-Open No. 2003-014933 discloses a transverse stretching machine called a tenter that stretches in the lateral direction by fixing both ends of the web with clips and pins and expanding the distance between the clips and pins in the lateral direction. It is described that can be preferably used.
Further, in this publication, in order to stretch or shrink in the longitudinal direction, the simultaneous biaxial stretching machine is used to expand or contract the interval in the transport direction of clips and pins in the transport direction (vertical direction). It is also disclosed that
Further, in this publication, when the clip portion is driven by the linear drive system, it is possible to smoothly stretch and reduce the risk of breakage, etc., and a method of stretching in the longitudinal direction is preferable. It has been shown that a method of stretching in the longitudinal direction using a difference in peripheral speed between the two and making use of the difference in peripheral speed between the rolls can be used.
In addition, in this publication, these stretching methods can be used in combination, and the stretching process is performed in two or more stages, such as (longitudinal stretching, lateral stretching, longitudinal stretching) or (longitudinal stretching, longitudinal stretching). However, these techniques may be applied to the present invention.

  Japanese Patent Laid-Open No. 2003-004374 discloses that in order to prevent foaming of the tenter-dried web, improve detachability, and prevent dust generation, hot air from the dryer is applied to both edges of the web. In order not to hit, a technique is described in which the width of the dryer is formed shorter than the width of the web, and this technique may be employed in the present invention.

  Japanese Patent Application Laid-Open No. 2003-019757 discloses that the tenter drying web is prevented from being foamed, the releasability is improved, and dust is prevented from being generated. The technique which provides a wind-shielding board inside a part is described, You may employ | adopt this technique for this invention.

  Japanese Patent Application Laid-Open No. 2003-053749 discloses that the thickness after drying of both ends of a film carried by a pin tenter is X (μm) in order to stably carry and dry the film. When the average thickness after drying is T (μm), T ≦ 60 satisfies 40 ≦ X ≦ 200, and 60 <T ≦ 120, 40+ (T−60) × 0.2 ≦ X ≦ 300 Is satisfied, and in 120 <T, a technique that satisfies 52+ (T−120) × 0.2 ≦ X ≦ 400 is described, and this technique may be employed in the present invention.

  Japanese Patent Laid-Open No. 2-182654 discloses a tenter device in which a heating chamber and a cooling chamber are provided in a dryer of a multistage tenter so that wrinkles are not generated in the multistage tenter. A separate cooling technique is described and may be employed in the present invention.

  Japanese Patent Application Laid-Open No. 9-073315 describes a technique for increasing the inner pin density and decreasing the outer pin density in the pin tenter pins in order to prevent web breakage, wrinkles, and conveyance failure. This technique may be employed in the present invention.

  Japanese Patent Laid-Open No. 9-085846 discloses a web-type side edge holding pin in a tenter drying device in order to prevent foaming of the web itself and adhesion of the web to the holding means in the tenter. A technology is described in which the pin is cooled to below the foaming temperature of the web with a cooler, and the pin immediately before the web is entrapped is cooled to the gelation temperature of the dope + 15 ° C. or less in the duct type cooler. You may employ | adopt for this invention.

  Japanese Patent Laid-Open No. 2003-103542 discloses a surface of a web that cools the insertion structure and contacts the insertion structure in the pin tenter in order to prevent pin tenter loss and improve foreign matter. A technique relating to a solution casting method for preventing the temperature from exceeding the gelling temperature of the web is described, and this technique may be employed in the present invention.

Japanese Patent Application Laid-Open No. 11-077718 discloses a web in a tenter in order to prevent deterioration in quality such as flatness when the speed is increased by a solution casting method or the width of the web is widened by a tenter. Is dried, the wind speed is 0.5-20 (40) m / s, the transverse temperature distribution is 10% or less, the web up-down air volume ratio is 0.2-1 and the dry gas ratio is 30-250 J /. A technique of Kmol is described. Furthermore, preferable drying conditions are disclosed depending on the amount of residual solvent in drying in the tenter.
Specifically, after the web is peeled off from the support, the angle of the air blown from the air outlet is in the range of 30 to 150 ° with respect to the film plane until the amount of residual solvent in the web reaches 4% by mass. And when the wind speed distribution on the film surface located in the direction in which the drying gas is blown out is based on the upper limit value of the wind speed, the difference between the upper limit value and the lower limit value is within 20% of the upper limit value. When blowing out, drying the web, and when the residual solvent amount in the web is 70% by mass or more and 130% by mass or less, the wind speed on the web surface of the dry gas blown out from the blowing type dryer is 0.5 m. / Sec or more and 20 m / sec or less, and when the residual solvent amount is less than 70% by mass and 4% by mass or more, the drying gas blown out at a wind speed of 0.5 m / sec or more and 40 m / sec or less. When the temperature distribution of the drying gas in the width direction of the web is based on the upper limit value of the gas temperature, the difference between the upper limit value and the lower limit value should be within 10% of the upper limit value. When the solvent amount is 4% by mass or more and 200% by mass or less, the air flow ratio q of the dry gas blown out from the blow-out port of the blow-type dryer located above and below the web to be conveyed may be 0.2 ≦ q ≦ 1. Are listed.
Furthermore, as a preferred embodiment, at least one kind of gas is used for the drying gas, the average specific heat is 31.0 J / K · mol or more and 250 J / K · mol or less, and the room temperature contained in the drying gas during drying. And the concentration of the liquid organic compound is dried with a drying gas having a saturated vapor pressure of 50% or less. These techniques may be employed in the present invention.

Japanese Patent Application Laid-Open No. 11-0777719 discloses that a tenter clip has a built-in heating portion in a TAC (cellulose triacetate) film manufacturing apparatus in order to prevent deterioration of flatness and coating due to generation of contaminants. The technology is described.
As a further preferred aspect of this technique, a device for removing foreign matter generated at the contact portion between the clip and the web after the tenter clip releases the web and again supports the web is provided. Or, remove the foreign matter using a liquid and a brush, the residual amount at the time of contact between the clip or pin and the web is 12 mass% or more and 50 mass% or less, and the surface temperature of the contact portion between the clip or pin and the web is It is disclosed that it is 60 ° or more and 200 ° or less (more preferably 80 ° or more and 120 ° or less), and this technique may be adopted in the present invention.

  In addition, in JP-A-11-090943, in order to improve flatness, improve quality deterioration due to tearing in the tenter, and increase productivity, in the tenter clip, an arbitrary transport length Lt ( m) and the total length Ltt (m) in the conveyance direction of the portion where the clip of the tenter having the same length as Lt holds the web Lr = Ltt / Lt is 1.0 ≦ Lr ≦ 1 .99 is described. Further, as a preferred embodiment, a technique is disclosed in which a portion for holding a web is arranged without a gap when viewed from the web width direction, and this technique may be adopted in the present invention.

Japanese Patent Application Laid-Open No. 11-090944 discloses a plastic film manufacturing apparatus in front of a tenter entrance in order to improve flatness deterioration due to web sagging and introduction instability when a web is introduced into a tenter. Describes a technology having a sag suppressing device in the width direction of the web.
As a further preferable aspect of this technology, the sag suppressing device is a rotating roller that rotates in a direction range of 2 to 60 ° in the width direction, has an air intake device on the upper portion of the web, and from below the web. Having a blower capable of blowing air is also disclosed, and this technique may be employed in the present invention.

  Japanese Patent Laid-Open No. 11-090945 discloses that the web peeled off from the support is angled with respect to the horizontal in the manufacturing method of tack for the purpose of preventing the deterioration of quality and sagging which hinders productivity. Is introduced to the tenter, and this technology may be employed in the present invention.

  JP-A-2000-289903 discloses a transporting apparatus that transports while applying tension in the width direction of the web when the film is peeled and has a solvent content of 50 to 12% by mass in order to produce a film having stable physical properties. , A web width detecting means, a web holding means, and a technique that has two or more variable bending points, calculates a web width from a detection signal in web width detection, and changes the position of the bending point This technique may be employed in the present invention.

Japanese Patent Application Laid-Open No. 2003-033933 discloses that the right and left sides of the web on the left and right sides near the entrance of the tenter are provided in order to improve clipping, prevent web breakage for a long period of time, and obtain a film with excellent quality. A web side edge curl prevention guide plate is disposed at least below the upper and lower side edges, and the web facing surface of the guide plate is arranged in the web conveying direction and the web. It is described that it comprises a contact metal part.
As a further preferable aspect of this technique, the web contact resin portion of the guide plate facing the web is disposed on the upstream side in the web conveyance direction, and the web contact metal portion is disposed on the downstream side. The step between the resin part and the metal part for web contact (including the inclination) is within 500 μm, and the distance in the width direction in contact with the web of the resin part for web contact of the guide plate and the web of the metal part for web contact is The distance between the web contact resin part of the guide plate and the web contact metal part of the web contact direction in the web conveyance direction is 5 to 120 mm, respectively, and the web contact resin part of the guide plate is 2 to 150 mm. , Provided on the metal guide board by surface resin processing or resin coating, the web contact resin part of the guide plate is made of a single resin, the left and right sides of the web The distance between the web facing surfaces of the guide plates arranged above and below at the side edge is 3 to 30 mm, and between the web facing surfaces of the upper and lower guide plates at the left and right side edges of the web. The distance is increased in the width direction of the web and inward at a rate of 2 mm or more per width of 100 mm, and the upper and lower guide plates have a length of 10 to 300 mm at the left and right side edges of the web, respectively. And both upper and lower guide plates are arranged so as to be displaced back and forth along the web conveyance direction, and the distance of deviation between the upper and lower guide plates is −200 to +200 mm, The web facing surface of the upper guide plate is made of only resin or metal, the web contact resin portion of the guide plate is made of Teflon (registered trademark), and the web contact gold The genus part is made of stainless steel, the web facing surface of the guide plate or the surface roughness of the resin part for web contact and / or the metal part for web contact provided on this is 3 μm or less, etc. It is disclosed.
Further, it is also described that the installation position of the upper and lower guide plates for preventing web side edge curl generation is preferably between the peeling side end portion of the support and the tenter introduction portion, and more preferably installed near the tenter entrance. These techniques may be employed in the present invention.

Japanese Patent Application Laid-Open No. 11-048271 discloses a width stretching device at the time when the web has a solvent content of 50 to 12% by mass in order to prevent cutting and unevenness of the web during drying in the tenter. And a technique of applying a pressure of 0.2 to 10 KPa from both sides of the web by a pressurizing device when the solvent content of the web is 10% by mass or less.
As a more preferable embodiment of this technique, when applying the tension using a nip roll as a method of finishing applying the tension when the solvent content is 4% by mass or more and applying pressure from both sides of the web (film), a pair of nip rolls is used. It is also disclosed that about 1 to 8 pairs are preferable, and that the temperature when pressurizing is preferably 100 to 200 ° C., and this technique may be employed in the present invention.

Japanese Patent Application Laid-Open No. 2002-036266 discloses a preferred embodiment of a technique for obtaining a high-quality thin tack having a thickness of 20 to 85 μm as a difference in tension acting on the web along the conveying direction before and after the tenter. Is 8 N / mm ² or less, a preheating step for preheating the web after the peeling step, a stretching step for stretching the web using a tenter after the preheating step, and after the stretching step, And a relaxation step for relaxing by an amount smaller than the stretching amount in the stretching step, and the temperature T1 in the preheating step and the stretching step is set to (glass transition temperature Tg-60 of the film) or higher, and the relaxation step The temperature T2 in the process is set to (T1-10) ° C. or less, and the stretch ratio of the web in the stretching process is set to 0 to 30% in a ratio to the web width immediately before entering the stretching process. A web of stretch rate in the relaxation step, to -10 to 10%, etc. are disclosed, may be employed the technique of the present invention.

  JP 2002-225054 A discloses that the residual solvent amount of the web after peeling is 10% by mass for the purpose of being excellent in thinness and dry weight with a dry film thickness of 10 to 60 μm and small durability. Until both ends of the web are gripped by clips, drying shrinkage suppression by holding the width is performed and / or stretching in the width direction is performed, and the plane orientation degree S represented by the following formula is 0. Forming a film of .0008 to 0.0020 (in the following formula, Nx is the refractive index in the direction of the largest refractive index in the plane of the film, Ny is the refractive index in the direction perpendicular to the plane of Nx in the plane) , Nz refers to the refractive index in the film thickness direction of the film), the time from casting to peeling is 30 to 90 seconds, the web after peeling is stretched in the width direction and / or the longitudinal direction, Etc., and this technology is adopted in the present invention. It may be.

S = {(Nx + Ny) / 2} -Nz)

  Japanese Patent Application Laid-Open No. 2002-341144 discloses a solution film-forming method having a stretching process in which the mass concentration of a retardation increasing agent has a higher optical distribution as it approaches the center in the film width direction in order to suppress optical unevenness. This technique may be employed in the present invention.

In addition, in JP-A-2003-071863, in order to obtain a film in which fogging does not occur, the draw ratio in the width direction is preferably 0 to 100%, and when used as a polarizing plate protective film, It is described that 20% is more preferable, and 8 to 15% is still more preferable.
On the other hand, in the gazette, when used as a retardation film (optical compensation film), 10 to 40% is more preferable, 20 to 30% is most preferable, and Ro can be controlled by a draw ratio. It is disclosed that a higher value is preferable because the flatness of the finished film is excellent.
Furthermore, when the tenter is used, the residual solvent amount of the film is preferably 20 to 100% by mass at the start of the tenter, and drying is performed while the tenter is applied until the residual solvent amount of the film becomes 10% by mass or less. It is preferable that 5% by mass or less is more preferable.
Moreover, the drying temperature in the case of performing a tenter is preferably 30 to 150 ° C., more preferably 50 to 120 ° C., most preferably 70 to 100 ° C., and the lower the drying temperature, the transpiration such as the ultraviolet absorber and the plasticizer. However, it is also disclosed that the higher the drying temperature, the better the flatness of the film, and this technique may be employed in the present invention.

  Japanese Patent Application Laid-Open No. 2002-248639 discloses that a cellulose ester solution is continuously cast on a support in order to reduce vertical and horizontal dimensional fluctuations during storage under high temperature and high humidity conditions. In the method for producing a film to be peeled and dried, a technique for drying so that the drying shrinkage rate satisfies the following formula is described.

0 ≦ dry shrinkage (%) ≦ 0.1 × residual solvent amount when peeling (%)

  As a more preferred embodiment of this technique, when the residual solvent amount of the cellulose ester film after peeling is in the range of 40 to 100% by mass, at least the residual solvent amount is set to 30 while holding both ends of the cellulose ester film by tenter conveyance. The amount of residual solvent at the tenter transport inlet of the cellulose ester film after peeling is 40 to 100% by weight, the amount of residual solvent at the outlet is 4 to 20% by weight, and the cellulose ester by tenter transport The tension for transporting the film increases from the entrance to the exit of the tenter transport, the tension for transporting the cellulose ester film by the tenter transport and the tension of the cellulose ester film in the width direction are substantially equal, etc. And this technology is adopted in the present invention. It may be.

  Japanese Patent Application Laid-Open No. 2000-239403 discloses a residual solvent ratio X at the time of peeling and a residual value when introduced into a tenter in order to obtain a film having a thin film thickness and excellent optical isotropy and flatness. It is disclosed that the film formation is performed with the relationship with the solvent ratio Y being in the range of 0.3X ≦ Y ≦ 0.9X, and this technique may be employed in the present invention.

  JP 2002-286933 A includes a method of stretching a film to be formed by casting, a method of stretching under heating conditions and a method of stretching under solvent-containing conditions. When stretching, it is preferable to stretch at a temperature below the glass transition point of the resin. On the other hand, when stretching a cast film under solvent-impregnated conditions, the once dried film is re-solvent. It is disclosed that the film can be impregnated with a solvent to be stretched, and this technique can be employed in the present invention.

The metal support used in the casting step preferably has an arithmetic average roughness (Ra) of 0.015 μm or less and a ten-point average roughness (Rz) of 0.05 μm or less. The thickness (Ra) is preferably 0.001 to 0.01 μm, the ten-point average roughness (Rz) is more preferably 0.001 to 0.02 μm, and the (Ra) / (Rz) ratio is 0. More preferably, it is 15 or more.
Thus, by setting the surface roughness of the metal support within a predetermined range, the surface shape of the transparent support after film formation can be controlled within a preferable range described later.

  Furthermore, the cellulose acylate solution of the present invention may be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer).

<Characteristics of transparent support>
<< surface properties >>
The surface of the transparent support used in the present invention has an arithmetic average roughness (Ra) of surface irregularities of the film based on JIS B0601-1994 of 0.0001 to 0.05 μm and a maximum height (Ry) of 0. It is preferable that it is .0002-0.2 μm.
The concave and convex shapes on the film surface can be evaluated by an atomic force microscope (AFM).
By setting the surface state of the transparent support of the present invention within the size of the above-mentioned unevenness, the entire surface of the transparent support is stably and uniformly applied in the application of adhesion imparting to the surface of the transparent support described later. After processing, optical defects due to processing unevenness, coating unevenness and the like are eliminated.

Further, the dynamic friction coefficient of the transparent support used in the present invention is preferably 0.4 or less, and particularly preferably 0.3 or less. When the coefficient of dynamic friction is large, the transparent support is likely to generate dust as a result of being rubbed strongly with the transport roll, and foreign matter adheres to the transparent support, and the frequency of optical compensation film point defects and coating streaks is acceptable. It will exceed the value.
The dynamic friction coefficient can be measured by a steel ball method using a 5 mmφ steel ball.

The surface resistivity of the transparent support used in the present invention is preferably 1.2 × 10 ¹² Ω / □ or less, more preferably 1.0 × 10 ¹² Ω / □ or less, and It is particularly preferably 8 × 10 ¹² Ω / □ or less. By setting the surface resistivity within the range of the present invention, adhesion of foreign matters to the transparent support and the optical compensation film can be suppressed, and point defects and coating stripes of the optical compensation film can be reduced.

<< Mechanical properties of transparent support >>
[Tear strength]
The tear strength of the transparent support is preferably 3 to 50 g at 30 ° C. and 85% RH (relative humidity).

[Scratch strength]
Further, the scratch strength is preferably 1 g or more, more preferably 5 g or more, and still more preferably 10 g or more.
Within these ranges, the scratch resistance and handling properties of the surface of the transparent support can be maintained without problems.
Scratch strength can be evaluated by scratching the surface of the transparent support using a sapphire needle having a cone apex angle of 90 degrees and a tip radius of 0.25 m, and with a load (g) at which the scratch mark can be visually confirmed. .

<< Hygroscopic expansion coefficient of transparent support >>
The hygroscopic expansion coefficient of the transparent support used for the optical compensation film of the present invention is preferably 30 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is preferably 15 × 10 ⁻⁵ /% RH or less, and more preferably 10 × 10 ⁻⁵ /% RH or less.
Moreover, although the one where a hygroscopic expansion coefficient is smaller is preferable, it is a value of 1.0 * 10 < ^-5 > /% RH or more normally. The hygroscopic expansion coefficient indicates the amount of change in the length of the sample when the relative humidity is changed at a constant temperature.
By adjusting the hygroscopic expansion coefficient, it is possible to prevent frame-like transmittance increase, that is, light leakage due to distortion, while maintaining the optical compensation function of the optical compensation film.

Here, a method for measuring the hygroscopic expansion coefficient in the present embodiment will be described below.
First, a sample having a width of 5 mm and a length of 20 mm was cut out from the produced transparent support, and one end was fixed and hung in an atmosphere of 25 ° C. and 20% RH (R ₀ ). A weight of 0.5 g was hung from the other end and left for 10 minutes to measure the length (L ₀ ). Next, the length (L ₁ ) was measured while maintaining the temperature at 25 ° C. and the humidity at 80% RH (R ₁ ). The hygroscopic expansion coefficient was calculated by the following equation. The measurement was performed 10 samples for the same sample, and the average value was adopted.

Hygroscopic expansion coefficient [/% RH] = {(L ₁ −L ₀ ) / L ₀ } / (R ₁ −R ₀ )

  In order to reduce the dimensional change due to moisture absorption of the produced transparent support, it is preferable to add a compound having a hydrophobic group or fine particles. As the compound having a hydrophobic group, a material corresponding to a plasticizer or a degradation inhibitor having a hydrophobic group such as an aliphatic group or an aromatic group in the molecule is particularly preferably used. It is preferable that the addition amount of these compounds exists in the range of 0.01-10 mass% with respect to the solution (dope) to adjust.

<Residual solvent amount of transparent support>
Curling can be suppressed by setting the residual solvent amount of the transparent support used in the present invention to 1.5% or less. The residual solvent amount is more preferably 1.0% or less.
This is presumably because the main effect factor is that the free volume is reduced by reducing the amount of residual solvent during film formation by the solvent casting method described above.
Specifically, it is preferable that the residual solvent amount with respect to the transparent support is dried under the condition of 0.01 to 1.5% by mass, and under the condition of 0.01 to 1.0% by mass. More preferably, it is dried.
In the present invention, the residual solvent amount is a volatile content relative to the solid content mass, and is a value represented by the following formula. In the following formula, W represents the sample soft film mass, and W ₀ represents the sample mass after the sample soft film W is dried at 110 ° C. for 2 hours.

Residual solvent amount (% by mass) = ((W−W ₀ ) / W ₀ ) × 100

<Water permeability of optical compensation film>
Here, the water vapor permeability of the transparent protective film and the optical compensation film of the present invention is 100 to 2,000 g / m ² · 24 h in JIS standard JISZ0208, condition B (temperature 40 ° C., humidity 90% RH).
According to the conventional knowledge, if it exceeds 150 g / m ² · 24 h, the absolute value of the humidity dependency of the Re value and Rth value of the transparent support tends to exceed 0.5 nm /% RH, which is not preferable. However, the cellulose acylate film containing the compound A of the present invention can suppress the dependency of the Re value and the Rth value on the humidity even if the moisture permeability is high.

  The method of measuring moisture permeability is described in “Polymer Properties II” (Polymer Experiment Course 4 Kyoritsu Shuppan) p. 285-294: The method described in the measurement of the amount of vapor permeation (mass method, thermometer method, vapor pressure method, adsorption amount method) can be applied.

<Water content of optical compensation film>
The water content of the transparent support constituting the transparent protective film and optical compensation film of the present invention is 30 ° C., 85 ° C. regardless of the film thickness, so as not to impair the adhesiveness with a water-soluble polymer such as polyvinyl alcohol. It is preferable that it is 0.3-12 g / m < ² > under% RH. Here too, the cellulose acylate film containing the compound A of the present invention has a higher moisture content than a film not containing it, but is different from conventional knowledge in that the humidity dependency is improved.

<Optical anisotropy of transparent support>
The transparent support used for the optical compensation film of the present invention exhibits optical anisotropy, and represents the Re retardation value (in-plane retardation value) and Rth retardation value (thickness direction retardation value). ) Are defined by the following formulas (a) and (b), respectively.
In the following formulas (a) and (b), nx is the refractive index in the slow axis direction in the plane of the transparent support, and ny is the fast axis in the plane of the transparent support. The refractive index in the direction, nz is the refractive index in the thickness direction of the transparent support, and d is the thickness of the transparent support.

Re = (nx−ny) × d... Formula (a)
Rth = {(nx + ny) / 2−nz} × d (Equation (b)

In the present invention, the Re retardation value of the transparent support is preferably in the range of 4 to 200 nm, and more preferably in the range of 10 to 100 nm. Further, the Rth retardation value is preferably in the range of 50 to 400 nm, and more preferably in the range of 100 to 200 nm.
In addition, it is preferable that the birefringence ((DELTA) n: nx-ny) of a transparent support body is 0.000025-0.0088 with respect to wavelength 550nm, and 0.0003-0.005 is more preferable.
The birefringence {(nx + ny) / 2−nz} in the thickness direction is preferably 0.0006 to 0.02, more preferably 0.001 to 0.007 with respect to the wavelength of 550 nm.

Furthermore, the transparent support of the present invention satisfies the following formulas (3) to (6).
0.5 ≦ Re (450) / Re (550) ≦ 1.0 (3)
1.0 <= Re (630) / Re (550) <= 1.5 ... Formula (4)
1.0 ≦ Rth (450) / Rth (550) ≦ 1.5... Equation (5)
0.5 ≦ Rth (630) / Rth (550) ≦ 1.0... (6)
In addition, it is preferable that Formula (3) exists in the range of 0.5 or more and 1.0 or less, and it is more preferable that it exists in the range of 0.5 or more and 0.9 or less.
Moreover, it is preferable that Formula (4) exists in the range of 1.0 or more and 1.5 or less, and it is more preferable that it exists in the range of 1.0 or more and 1.45 or less.
Moreover, it is preferable that Formula (5) exists in the range of 1.0 or more and 1.5 or less, and it is more preferable that it exists in the range of 1.0 or more and 1.3 or less.
Moreover, it is preferable that Formula (6) exists in the range of 0.5 or more and 1.0 or less, and it is more preferable that it exists in the range of 0.6 or more and 1.0 or less.
In the above formulas (3) to (6), Re (λ) is the retardation value of the optical compensation film with respect to light with a wavelength of λnm, and Rth (λ) is the optical with respect to light with a wavelength of λnm. It is the retardation value in the thickness direction of the compensation film.

Furthermore, the transparent support of the present invention is characterized by satisfying the following formulas (c) and (d).
0 nm <Δ (Re (10% RH) −Re (80% RH)) <15 nm Formula (c)
0 nm <Δ (Rth (10% RH) −Rth (80% RH)) <15 nm Formula (d)
However, in the above formulas (c) to (d), Re (10% RH) and Re (80% RH) are optical characteristics of the transparent support in an environment of 25 ° C. 10% and 25 ° C. 80% humidity, respectively. Rth (10% RH) and Rth (80% RH) are the retardation values when the humidity is adjusted until the temperature changes sufficiently. The transparent support is 25 ° C. 10% and 25 ° C. 80% humidity environment respectively This is the retardation value in the thickness direction when the humidity is adjusted until the optical characteristics change sufficiently.
The range of the formula (c) and the formula (d) is preferably 0 to 15 nm, more preferably 0 to 10 nm, and further preferably 0 to 5 nm.

In particular, as the transparent support of the optical compensation film used in the TN mode, the Re retardation value is preferably 4 to 40 nm, and the Rth retardation value is preferably in the range of 50 to 200 nm. OCB, HAN, VAN, As a transparent support of an optical compensation film used in an ECB mode such as a homogeneous alignment mode, the Re retardation value is preferably in the range of 10 to 70 nm, and the Rth retardation value is preferably in the range of 70 to 400 nm.
In the case of a transparent protective film that does not actively impart an optical compensation function, the Re retardation value is preferably in the range of 0 to 40 nm, and the Rth retardation value is preferably in the range of 0 to 200 nm.

<Method of imparting adhesion of transparent support>
The transparent support of the optical compensation film of the present invention is formed by further aligning and fixing an optical compensation layer made of a liquid crystalline substance on the alignment film. When the alignment film is provided by a coating method, the transparent support It is preferable to perform surface treatment so that adhesion is imparted to the surface of the body and the coating liquid for alignment film is uniformly applied.
Examples of the surface treatment method include a method of providing an undercoat layer of the alignment film.
As a method for providing an undercoat layer of the alignment film, for example, an undercoat layer described in JP-A-7-333433 or a resin layer such as gelatin containing both a hydrophobic group and a hydrophilic group is applied. And a single layer method.
In addition, a hydrophilic resin such as gelatin is provided as a first layer that is well adhered to the polymer film (hereinafter referred to as the first undercoat layer), and is further adhered to the alignment film as the second layer thereon. There is a so-called multi-layer method in which a layer (hereinafter abbreviated as an undercoat second layer) is applied. This multi-layer method is described, for example, in JP-A-11-248940.

<< Surface treatment of transparent support >>
Since the transparent support of the present invention is a thin layer film, it is preferable that the surface of the transparent support is directly subjected to a hydrophilic treatment.
Examples of the surface treatment include corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, acid treatment, and alkali saponification treatment. Alkali saponification is more preferable.

[Alkaline saponification]
The alkali saponification treatment is preferably performed by immersing, spraying or coating an alkaline solution on a transparent support, and the saponification treatment is preferably performed by coating.

-Alkaline solution-
In the present invention, the alkaline solution used for the alkaline saponification treatment preferably has a pH of 11 or more, and more preferably has a pH of 12-14.
Examples of the alkali agent used in the alkali solution include sodium hydroxide, potassium, lithium and the like as the inorganic alkali agent.
Examples of the organic alkali agent include diethanolamine, triethanolamine, DBU (1,8-diazabicyclo [5,4,0] -7-undecene), DBN (1,5-diazabicyclo [4,3,0] -5. -Nonene), tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylbutylammonium hydroxide, and the like.
These alkali agents may be used alone or in combination of two or more, and may be added in the form of a salt, for example, a part of which is halogenated.
Among these alkali agents, sodium hydroxide or potassium hydroxide is preferable because the pH can be adjusted in a wide pH range by adjusting these amounts.
The concentration of the alkaline solution is determined according to the type of alkaline agent to be used, the reaction temperature and the reaction time, and the content of the alkaline agent is preferably 0.1 to 5 mol / Kg in the alkaline solution. 0.5-3 mol / Kg is more preferable.

The alkaline solution solvent of the present invention preferably comprises a mixed solution of water and a water-soluble organic solvent.
As the organic solvent, any organic solvent miscible with water can be used. An organic solvent having a boiling point of 120 ° C. or lower is preferable, and an organic solvent having a boiling point of 100 ° C. or lower is particularly preferable.
Among them, preferred organic solvents are those having an inorganic / organic value (I / O value) of 0.5 or more and a solubility parameter in the range of 16 to 40 (mJ / m ³ ).
More preferably, the I / O value is 0.6 to 10, and the solubility parameter is 18 to 31 (mJ / m ³ ).
If the I / O value is more inorganic than this range or the solubility parameter is low, the alkali saponification rate decreases, and the overall uniformity of the saponification degree becomes unsatisfactory.
On the other hand, if the I / O value is more organic than the above range or the solubility parameter is high, the saponification rate is fast, but haze is likely to occur, and therefore the overall uniformity is similarly unsatisfactory.

In addition, when an organic solvent, particularly an organic solvent in each range of organic and soluble, is used in combination with a surfactant or a compatibilizer described later, a high saponification rate is maintained and the saponification degree over the entire surface is maintained. Uniformity is improved.
Organic solvents having preferable characteristic values are described in, for example, “Synthetic Organic Chemistry Association”, “New Edition Solvent Pocket Book” (Ohm Co., Ltd., published in 1994). For the inorganic / organic value (I / O value) of the organic solvent, see, for example, Yoshio Koda “Organic Conceptual Diagram” (Sankyo Publishing Co., Ltd., 1983) p. 1-31.

  Specifically, monohydric aliphatic alcohols (methanol, ethanol, propanol, isopropanol, butanol, pentanol, etc.), divalent aliphatic alcohols (ethylene glycol, propylene glycol, etc.), alicyclic alkanols (cyclohexanol, Methylcyclohexanol, methoxycyclohexanol, cyclohexylmethanol, cyclohexylethanol, cyclohexylpropanol, etc.), phenylalkanols (benzyl alcohol, phenylethanol, phenylpropanol, phenoxyethanol, methoxybenzyl alcohol, benzyloxyethanol, etc.), heterocyclic alkanols (Furfuryl alcohol, tetrahydrofurfuryl alcohol, etc.), monoethers of glycol compounds (methylcellsol) , Ethyl cellosolve, propyl cellosolve, butyl cellosolve, hexyl cellosolve, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, methoxytriglycol, ethoxytriglycol, propylene glycol monomethyl ether, propylene glycol monoethyl Ethers, propylene glycol monopropyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), amides (N, N-dimethylformamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3 dimethylimidazolide) Non), sulfoxides (dimethyl sulfoxide, etc.) and ethers (tetrahydrofuran, pyran, dioxane, trioxane, dimethyl cellosolve, diethyl) Cellosolve, dipropyl cellosolve, methyl ethyl cellosolve, dimethyl carbitol, dimethyl carbitol, methyl ethyl carbitol, etc.) and the like. The organic solvent to be used may be used alone or in combination of two or more.

When at least one organic solvent is used alone or in combination of two or more organic solvents, those having high solubility in water are preferable. The solubility of water in the organic solvent is preferably 50% by mass or more, and more preferably freely mixed with water. This makes it possible to prepare an alkaline solution having sufficient solubility in an alkali agent, a salt of a fatty acid by-produced by a saponification treatment, a carbonate salt generated by absorbing carbon dioxide in the air, and the like.
The use ratio of the organic solvent in the solvent is determined according to the type of the solvent, the miscibility (solubility) with water, the reaction temperature and the reaction time.
The mixing ratio (mass ratio) of water and organic solvent is preferably 3/97 to 85/15, more preferably 5/95 to 60/40, and further preferably 15/85 to 40/60. Within these ranges, the entire surface of the transparent support is easily saponified uniformly without impairing the optical properties of the acylate film.

  As the organic solvent contained in the alkaline solution used in the present invention, an organic solvent (for example, fluorinated alcohol) different from the organic solvent having the above-mentioned preferable I / O value is dissolved in a surfactant and a compatibilizer described later. You may use together as an adjuvant. The content is preferably 0.1 to 5% with respect to the total mass of the liquid used.

The alkaline solution used in the present invention preferably contains a surfactant. By adding a surfactant, the surface tension can be lowered to facilitate coating, and the uniformity of the coating film can be increased to prevent cissing failure, and haze that tends to occur in the presence of an organic solvent is suppressed. Progress evenly.
The effect becomes particularly remarkable by the coexistence of a compatibilizer described later.
The surfactant used is not particularly limited, and may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a fluorosurfactant, and the like. .

Specifically, for example, Tokiyuki Yoshida “Surfactant Handbook (new edition)” (Engineering Books, published in 1987), “Functional Creation / Material Development / Applied Technology of Surfactant”, Volume 1 (Technical Education Publishing) , Published in 2000) and the like.
Among these surfactants, quaternary ammonium salts as cationic surfactants, various polyalkylene glycol derivatives as nonionic surfactants, polyethylene oxide derivatives such as various polyethylene oxide adducts, Betaine-type compounds as amphoteric surfactants are preferred.
It is preferable to use a nonionic activator and an anionic activator or a nonionic activator and a cationic activator together in the alkaline solution because the effects of the present invention are enhanced.

  0.001-10 mass% is preferable and, as for the addition amount with respect to the alkaline solution of these surfactant, 0.01-5 mass% is more preferable.

  The alkaline solution used in the present invention preferably contains a compatibilizing agent. In the present invention, the “compatibilizer” refers to a hydrophilic compound having a water solubility of 50 g or more with respect to 100 g of the compatibilizer at a temperature of 25 ° C. The solubility of the water of the compatibilizing agent is preferably 80 g or more, more preferably 100 g or more with respect to 100 g of the compatibilizing agent. When the compatibilizer is a liquid compound, the boiling point is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher.

The compatibilizing agent has an action of preventing drying of the alkaline solution attached to a wall surface such as a bath for storing the alkaline solution, suppressing fixation, and stably holding the alkaline solution. Also, after applying the alkali solution to the surface of the transparent support and holding it for a certain period of time, until the saponification treatment is stopped, the applied alkali solution thin film is dried, causing precipitation of solids, and the water washing step It has the effect of preventing difficulty in washing out the solid matter in Furthermore, phase separation between water as a solvent and the organic solvent is prevented.
In particular, the coexistence of the surfactant, the organic solvent, and the compatibilizer described above allows the treated transparent support to have a low haze and be stable and uniform even in the case of a long continuous saponification treatment. The degree of saponification.

The compatibilizing agent is not particularly limited as long as it is a material that satisfies the above conditions, and for example, a water-soluble polymer containing a repeating unit having a hydroxyl group and / or an amide group such as a polyol compound and a saccharide is preferable. .
As the polyol compound, any of a low molecular compound, an oligomer compound, and a polymer compound can be used. Specific examples of the polyol compound are given below.
Examples of aliphatic polyols include alkane diols having 2 to 8 carbon atoms and alkanes having 3 to 18 carbon atoms containing 3 or more hydroxyl groups.
Examples of the alkanediol having 2 to 8 carbon atoms include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin monomethyl ether, glycerin monoethyl ether, cyclohexanediol, cyclohexanedimethanol, diethylene glycol, and dipropylene glycol. Etc.
Examples of the alkane having 3 to 18 carbon atoms and containing 3 or more hydroxyl groups include, for example, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, diglycerin, dipentaerythritol. And inositol.

As the polyalkyleneoxy polyols, the same alkylene diols as described above may be bonded to each other, or different alkylene diols may be bonded to each other, but a polyalkylene polyol in which the same alkylene diols are bonded to each other is more preferable. .
In any case, the number of bonds is preferably 3 to 100, and more preferably 3 to 50. Specific examples include polyethylene glycol, polypropylene glycol, and poly (oxyethylene-oxypropylene).

Examples of saccharides include “Natural Polymers” Chapter 2 (Kyoritsu Shuppan Co., Ltd., published in 1984) edited by the Society of Polymer Science, Japan, “Modern Industrial Chemistry 22, Natural Products Industrial Chemistry”. II "(Asakura Shoten Co., Ltd., published in 1967) and the like. Among them, saccharides that do not have free aldehyde groups and ketone groups and do not exhibit reducibility are preferred.
The saccharides are generally classified into glucose, sucrose, trehalose-type oligosaccharides in which reducing groups are bonded, glycosides in which saccharide reducing groups and non-saccharides are combined, and sugar alcohols reduced by hydrogenation of saccharides. However, both can be suitably used in the present invention.
Examples of the saccharide include saccharose, trehalose, alkyl glycoside, phenol glycoside, mustard oil glycoside, D, L-arabit, ribit, xylit, D, L-sorbit, D, L-mannite, Examples include D, L-exit, D, L-talit, zurisit, allozulcit, and reduced water candy. These saccharides can be used alone or in combination of two or more.

Examples of the water-soluble polymer having a hydroxyl group and / or an amide group and having a repeating unit include natural gums (for example, gum arabic, guar gum, tragand gum, etc.), polyvinyl pyrrolidone, dihydroxypropyl acrylate Examples thereof include addition reactants of coalescence, celluloses, or chitosans and epoxy compounds (ethylene oxide or propylene oxide).
Among these, polyol compounds such as alkylene polyols, polyalkyleneoxy polyols and sugar alcohols are preferable.
Moreover, it is preferable that it is 0.5-25 mass% with respect to an alkaline solution, and, as for content of a compatibilizing agent, it is more preferable that it is 1-20 mass%.

  The alkaline solution used in the present invention may contain other additives. Examples of other additives include known ones such as antifoaming agents, alkaline solution stabilizers, pH buffering agents, preservatives, and antibacterial agents.

-Alkaline saponification method-
The surface treatment method of the transparent support using the above alkali solution may be any conventionally known method, and it is preferable to immerse in an alkali solution or to apply an alkali solution, and particularly, only one surface of the transparent support. The coating method is preferable when the saponification treatment is uniformly performed without unevenness.
As a coating method, a conventionally known coating method can be used. For example, a die coater (extrusion coater, slide coater, slit coater), roll coater (forward roll coater, reverse roll coater, gravure coater), rod coater, A blade coater or the like can be preferably used.

The saponification treatment is preferably performed at a treatment temperature in a range not exceeding 120 ° C. at which the deformation of the transparent support to be treated and the alteration of the treatment liquid do not occur.
Further, the treatment temperature is preferably in the range of 10 to 100 ° C, more preferably 20 to 80 ° C.
The time for the saponification treatment is determined by appropriately adjusting the alkali solution and the treatment temperature, but it is preferably performed in the range of 1 to 60 seconds.
Further, the step of saponifying the transparent support with an alkali solution at a temperature of at least 10 ° C. on the surface, the step of maintaining the temperature of the transparent support at least 10 ° C., and washing off the alkaline solution from the transparent support. It is preferable to carry out an alkali saponification treatment according to the process.

In the treatment for saponifying the surface of the transparent support with an alkaline solution at a predetermined temperature, a step of adjusting the temperature to a predetermined temperature before coating, a step of adjusting the alkaline liquid to a predetermined temperature in advance, or these The process etc. which combined these are mentioned. Among these, it is preferable to combine with a step of adjusting to a predetermined temperature before application.
The reaction process of the saponification treatment is to make the treatment process semi-sealed or sealed structure, in order to suppress the deterioration of the alkaline solution by carbon dioxide gas and extend the life of the liquid, and to introduce inert gas (nitrogen gas, argon gas, etc.), etc. It is preferable to carry out.
After the saponification reaction, it is preferable to wash and remove the alkali solution and the reaction product of the saponification treatment from the surface of the transparent support by washing with water, neutralizing, washing with water and the like.

20-55 degreeC is preferable and, as for the contact angle with the water of the transparent support body after surface treatment, 25-45 degreeC is more preferable. The surface energy is preferably 55 mN / m or more, and more preferably 55 to 75 mN / m.
The surface energy of the transparent support can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (Realize, 1989.12.10). Among these, it is preferable to use the contact angle method.
Specifically, in this contact angle method, two kinds of solutions having known surface energies are dropped onto a transparent support, and at the intersection of the surface of the liquid drop and the surface of the transparent support, In this method, the surface angle of the transparent support is defined as the contact angle, and the surface energy of the transparent support is calculated by calculation.

<Alignment film>
The alignment film of the present invention is preferably an alignment film formed by applying an organic compound (preferably polymer) coating solution. A cured polymer film is preferred from the viewpoint of the strength of the alignment film itself and the adhesion to the optically anisotropic layer as the lower layer or the upper layer. The alignment film is provided in order to define the alignment direction of the liquid crystal compound provided thereon. Examples of the method for defining the orientation include conventionally known methods such as rubbing, application of a magnetic field or electric field, and light irradiation.

The alignment film used in the present invention can correspond to the type of display mode of the liquid crystal cell.
In display modes such as VA, OCB, and HAN, in which many of the rod-like liquid crystalline molecules in the liquid crystal cell are oriented substantially vertically, the liquid crystalline molecules of the optically anisotropic layer are oriented substantially horizontally. It has a function.
On the other hand, in a display mode such as STN where many rod-like liquid crystalline molecules in a liquid crystal cell are oriented substantially horizontally, the function of aligning the liquid crystalline molecules of the optically anisotropic layer substantially vertically. Have.
In addition, in a display mode in which many rod-like liquid crystalline molecules in the liquid crystal cell such as TN are substantially obliquely oriented, the function of orienting the liquid crystalline molecules of the optically anisotropic layer substantially obliquely is provided. Have.

Specific types of polymers used in the alignment film of the present invention are described in the literature on optical compensation films using discotic liquid crystalline molecules corresponding to the various display modes described above.
As the polymer used for the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.
Examples of the polymer include compounds described in paragraph [0022] of JP-A-8-338913. Among these, water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, among which gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable. Most preferred are polyvinyl alcohol and modified polyvinyl alcohol.
The saponification degree of polyvinyl alcohol is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and most preferably 85 to 95 mol%. Moreover, it is preferable that the polymerization degree of polyvinyl alcohol is 100-3,000.

The modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification, or block polymerization modification.
Examples of the modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine Atom-substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy) and the like can be mentioned.
Specific examples of these modified polyvinyl alcohol compounds include, for example, paragraph number [0074] of JP-A No. 2000-56310, paragraph numbers [0022] to [0145] of JP-A No. 2000-155216, and JP-A No. 2002-62426. And the like described in paragraph Nos. [0018] to [0022] of the Gazette.

  Examples of the crosslinking agent of the polymer (preferably water-soluble polymer, more preferably polyvinyl alcohol or modified polyvinyl alcohol) used for the alignment film include aldehyde, N-methylol compound, dioxane derivative, and carboxyl group activation. , Active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specifically, for example, compounds described in paragraphs [0023] to [0024] of JP-A No. 2002-62426 may be mentioned. Among them, an aldehyde having a high reaction activity, particularly glutaraldehyde is preferable.

0.1-20 mass% is preferable with respect to a polymer, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable.
The amount of unreacted crosslinking agent remaining in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. If the crosslinking agent remains in the alignment film in an amount exceeding 1.0% by mass, sufficient durability cannot be obtained. When such an alignment film is used in a liquid crystal display device, reticulation may occur when used for a long time or when left in a high temperature and high humidity atmosphere for a long time.
The alignment film is basically formed by applying a coating solution containing the polymer, a crosslinking agent and a specific carboxylic acid, which is a composition for forming an alignment film, onto a transparent support, followed by drying by heating (crosslinking), and an alignment treatment. This is a cured film that can be formed.
As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming composition, the coating solution is preferably a mixed solvent of an organic solvent (eg, methanol) having a defoaming action and water. The ratio of water: methanol is preferably from 0: 100 to 99: 1, and more preferably from 0: 100 to 91: 9, by mass ratio. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an alignment film and also an optically anisotropic layer reduces remarkably.

The coating method of the alignment film is preferably a spin coating method, dip coating method, curtain coating method, die coating method (extrusion coating method, slide coating method, slit coating method, etc.), rod coating method, or roll coating method. In particular, a rod coating method and a die coating method are preferable.
The film thickness after drying is preferably 0.1 to 10 μm. Heat drying can be performed at 20-110 degreeC. In order to form sufficient crosslinking, 60 to 100 ° C is preferable, and 80 to 100 ° C is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 to 30 minutes.

Furthermore, after the coating liquid containing the composition for forming an alignment film of the present invention is applied to a transparent support, dried, and oriented by an orientation means, when the coating liquid for an optically anisotropic layer is applied, The surface of the alignment film is preferably maintained in the range of pH 2.0 to 6.9, and more preferably in the range of pH 2.5 to 5.0.
Further, when applying the coating liquid for the optically anisotropic layer, it is preferable that the fluctuation range ΔpH of the pH of the alignment film surface in the coating width direction is within a range of ± 0.30. More preferably, the pH is in the range of ± 0.15.
The method for measuring the pH value of the surface of the alignment film is that the sample coated with the alignment film is allowed to stand for 1 day in an environment of (temperature 25 ° C./humidity 65% RH), and then 10 mL of pure water in a nitrogen atmosphere It is carried out by placing and immediately reading the pH value with a pH meter.
The specification of the pH value of the surface of the alignment film of the present invention and the control of ΔpH in the coating width direction can be achieved by coating by the above rod coating method. Furthermore, it is also effective to appropriately adjust the drying temperature of the surface of the alignment film, the air volume when using the drying air, the air direction, and the like.

<Rubbing treatment>
The rubbing process is performed by rubbing the surface of the alignment film several times in a certain direction with paper or cloth. At this time, it is preferable to use a cloth in which fibers having uniform length and thickness are uniformly planted.
In the present invention, the rubbing treatment is a state in which the roll on which the cloth is pasted is arranged at an arbitrary angle with the transport direction of the transparent support provided with the alignment film, and the hair tip on which the cloth is planted contacts the alignment film Thus, the roll is rotated at a speed of 100 to 100,000 times / min while the transparent support is fed at a speed of 1 to 100 m / min.
The angle formed between the roll and the transport direction (longitudinal direction) of the transparent support can be arbitrarily adjusted. The angle is preferably in the range of 45 to 90 °, and the adjusted angle is It is more preferable to control within a range of ± 5 °.

In the rubbing treatment of the alignment film of the present invention, it is preferable that the temperature and humidity are controlled to be constant in order to rub in a uniform and stable alignment state. Specifically, it is preferable to control the temperature to be 20 to 28 ° C. and the humidity to be less than 35 to 60% RH. In particular, it is preferable to perform the humidity at 35 to 50% RH.
Also, when the surface of the alignment film is rubbed with a rubbing cloth, static electricity is generated due to friction between the rubbing cloth and the alignment film, and the generated static electricity is charged on the surface of the alignment film. It causes adsorption on the surface of the film. If dust adheres to the surface of the alignment film, the alignment state of the liquid crystal by the alignment film becomes non-uniform, or the visibility deteriorates such as optical point defects.

As a countermeasure against the static electricity, using an ion bar that generates ions of the opposite polarity to the static electricity charged on the alignment film, a soft X-ray irradiation, etc. It is preferable to remove the attached dust and the like with an ultrasonic dust remover before and after the rubbing treatment on the alignment film. This method is described, for example, in JP-A-7-333613 and JP-A-11-305233.
Further, when the long roll is continuously processed, the surface potential is detected so that the charging potential of the rubbing cloth does not exceed | 1 | KV, and the rubbing cloth is discharged so as not to exceed this charging amount. It is preferable. The charging potential of the rubbing cloth is preferably | 0.5 | KV or less, more preferably 0 to | 0.2 | KV. The sign of the electric charge is determined by the combination of the alignment film and the rubbing material.

Further, as a wet method, as described in JP-A-2001-38306, in a state in which a rubbed web is running, it is wetted with a liquid, preferably a solvent such as fluorinate, hexane, toluene or the like that does not swell the alignment film. A method of performing a wet dust removal treatment (a dust removal method after rubbing) in which a liquid, preferably a previously used solvent, is sprayed on the surface continuously rubbed with the elastic body after rubbing against the elastic body. preferable.
By the above method, optical defects due to disorder of alignment and adhesion of foreign matters are reduced or eliminated.

<Optically anisotropic layer>
An optical compensation film having an optically anisotropic layer is preferably used for canceling the birefringence of a liquid crystal cell composed of a nematic liquid crystal exhibiting bend alignment, hybrid alignment, etc., and the configuration and principle thereof are described in Japanese Patent No. 3118197. Details are shown.

  The optical compensation film having the optically anisotropic layer cancels the birefringence caused by the liquid crystal cell, so that the rubbing direction of the nematic liquid crystal in the liquid crystal cell and the retardation of the optically anisotropic layer of the optical compensation film are minimized. It is preferable that the direction of the value be parallel to the direction orthogonally projected onto the sheet surface.

As the liquid crystalline compound used for the optically anisotropic layer, a rod-like liquid crystalline compound or a discotic liquid crystalline compound (also referred to as a discotic liquid crystalline compound) can be used.
Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
These low-molecular liquid crystal compounds preferably have a polymerizable group in the molecule (for example, described in paragraph No. [0016] of JP-A No. 2000-304932).
Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used.
The high molecular liquid crystalline compound is a polymer having a side chain corresponding to the above low molecular liquid crystalline compound. An optical compensation film using a polymer liquid crystalline compound is described in JP-A-5-53016.

As the liquid crystal compound, a discotic liquid crystal compound is preferable.
Further, the surface of the discotic structural unit of the discotic liquid crystalline compound is inclined with respect to the surface of the transparent support, and the angle formed between the surface of the discotic structural unit and the surface of the transparent support is an optically anisotropic layer. It is preferable to change in the depth direction.
Such an optically anisotropic layer is obtained by providing an alignment film on a transparent support, laminating a layer made of a liquid crystalline compound thereon, and polymerizing a discotic liquid crystalline compound, for example. It can be formed by fixing the orientation.

  Discotic liquid crystalline compounds are described in various documents. For example, “C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981)”, “The Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal Chemistry, No. 5. Chapter 10, Chapter 2 Section (1994), “B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985)”, and “J. Zhang et al., J. Chem. Am. Chem. Soc., Vol. 116, page 2655 (1994) ". The polymerization of discotic liquid crystals is described in JP-A-8-27284.

In order to fix the discotic liquid crystalline compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic structural unit of the discotic liquid crystalline compound. The discotic structural unit and the polymerizable group are preferably discotic liquid crystalline compounds that are bonded via a linking group, whereby the alignment state can be maintained in the polymerization reaction.
The polymerizable group is preferably a polymerizable group selected from a radical polymerizable group or a cationic polymerizable group, and is an ethylenically unsaturated polymerizable group (such as an acryloyloxy group or a methacryloyloxy group) or an epoxy group. Most preferred. Examples of such compounds include compounds described in paragraphs [0151] to “0168” of JP-A No. 2000-155216.

Two or more kinds of discotic liquid crystalline compounds may be used in combination. For example, a polymerizable discotic liquid crystalline compound as described above and a non-polymerizable discotic liquid crystalline compound can be used in combination.
The non-polymerizable discotic liquid crystalline compound is preferably a compound in which the polymerizable group of the polymerizable discotic liquid crystalline compound is changed to a hydrogen atom or an alkyl group. That is, examples of the non-polymerizable discotic liquid crystalline compound include compounds described in Japanese Patent No. 2640083.

<Other additives of optically anisotropic layer>
In the optically anisotropic layer, in addition to the above liquid crystal compound, a plasticizer, a surfactant, a polymerizable monomer, etc. are used in combination to improve the uniformity of the coating film, the strength of the film, the orientation of the liquid crystal compound, etc. Can be improved. These additives are compatible with the liquid crystal compound, and the tilt angle of the liquid crystal molecules (for example, in the case of a discotic liquid crystal compound, the tilt angle from the surface of the transparent support of the surface of the disc-like structural unit) It is preferable that the change is given or the orientation is not hindered.

Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the polymerizable group-containing liquid crystalline compound. Examples thereof include those described in paragraph numbers [0018] to [0020] of JP-A No. 2002-296423. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.
Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraph numbers [0028] to [0056] of JP-A No. 2001-330725 are exemplified.

The polymer used together with the discotic liquid crystalline compound is preferably capable of changing the tilt angle of the discotic liquid crystalline molecule.
Examples of the polymer include cellulose acylate. Preferable examples of cellulose acylate include those described in JP-A 2000-155216, paragraph [0178].
In addition, it is preferable that the addition amount of the said polymer exists in the range of 0.1-10 mass% with respect to a liquid crystalline molecule so that the orientation of a liquid crystalline molecule may not be inhibited, The range of 0.1-8 mass% More preferably.
The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline compound is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.

<< Composition of optically anisotropic layer >>
The optically anisotropic layer is composed of a liquid crystalline compound, the following polymerizable initiator and any additive (eg, plasticizer, monomer, surfactant, cellulose acylate, 1,3,5-triazine compound, chiral agent). ) Is applied on the alignment film.
As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, Pyridine), hydrocarbons (eg, toluene, hexane), alkyl halides (eg, chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone), ethers (eg, tetrahydrofuran) 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
The coating liquid can be applied by a known method (eg, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method, wire bar coating method).

[Fixing the alignment state of liquid crystalline molecules]
The liquid crystalline molecules are preferably substantially uniformly aligned, more preferably fixed in a substantially uniformly aligned state, and the alignment of the liquid crystalline molecules is fixed by a polymerization reaction. More preferably. Examples of the polymerization reaction include a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and among these, the photopolymerization reaction is preferable.

Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α A hydrocarbon-substituted aromatic acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (described in US Pat. No. 3,046,127 and US Pat. No. 2,951,758), a triarylimidazole dimer and p -Combinations with aminophenyl ketones (described in U.S. Pat. No. 3,549,367), acridine and phenazine compounds (described in JP-A-60-105667 and U.S. Pat. No. 4,239,850), and oxadiazole compounds (Described in US Pat. No. 4,221,970) The
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.

Light irradiation for polymerization of discotic liquid crystalline molecules is preferably performed using ultraviolet rays.
Irradiation energy is preferably 20~5,000mJ / cm ^2, and more preferably 100 to 800 mJ / cm ^2.
In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. In the case of radical photopolymerization by light irradiation, it can be carried out in air or in an inert gas. It is preferable that the atmosphere be reduced.

  The thickness of the optically anisotropic layer is preferably 0.5 to 100 μm, more preferably 0.5 to 30 μm, and still more preferably 0.5 to 5 μm. However, depending on the mode of the liquid crystal cell, the optically anisotropic layer may be thickened (3 to 10 μm) in order to obtain high optical anisotropy.

  As described above, the alignment state of the liquid crystalline molecules in the optically anisotropic layer is determined according to the type of display mode of the liquid crystal cell. Specifically, the alignment state of the liquid crystalline molecules is controlled by the type of liquid crystalline molecules, the type of alignment film, and the use of additives (eg, plasticizer, binder, surfactant) in the optically anisotropic layer. The

<Slow axis angle of optical compensation film>
The optical compensation film of the present invention has in-plane anisotropy, and the optical anisotropy stretches a transparent support or a transparent support to which a retardation control agent has been added in advance, or an alignment film on the transparent support. Can be expressed by, for example, orienting the liquid crystal after rubbing.
In this case, the angle (slow axis angle) formed between the direction in which the refractive index is the largest in the plane (the direction of the slow axis) and the longitudinal direction (transport direction) of the optical compensation film in the form of a long roll is the stretching angle. Alternatively, it can be arbitrarily controlled from 0 to 90 ° depending on the rubbing angle.
The in-plane variation of the slow axis angle is preferably 3 ° or less, more preferably 2 ° or less, and more preferably 1 ° or less with respect to the average value of the slow axis angles. Further preferred.
Regarding the method of inclining the direction of the slow axis of the transparent support to a desired angle with respect to the transport method of the transparent support by stretching, JP-A-60-157831, JP-A-2-113920, It is described in Kaihei 3-124426, JP-A-3-182701, JP-A-4-164626, and JP-A-2000-9912.

<Surface treatment of optical compensation film>
In the present invention, the adhesion between the optical compensation film and the polarizing film is improved by surface-treating the surface of the optical compensation film on the side of the polarizing film. As the surface treatment, corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, acid treatment or alkali saponification treatment is used.
Examples of treatment methods such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, and acid treatment include the contents described in JIII Journal of Technical Disclosure No. 01-1745. In the present invention, alkali saponification treatment is preferred, and examples thereof include those having the same contents as [Alkali saponification treatment] in [Surface treatment of transparent support] described above.

(Polarizer)
The polarizing plate of the present invention has the above-described optical compensation film, a polarizing film (polarizer) on which the optical compensation film is disposed on one surface, and a transparent protective film disposed on the other surface of the polarizing film. Do it.

<Transparent protective film>
As the transparent protective film of the polarizing plate, the optical compensation film of the present invention and the other transparent support in a pair are used. Here, that the protective film is transparent means that the light transmittance is 80% or more.
In general, a cellulose acylate film is used as the transparent protective film.
The cellulose acylate film used as the transparent protective film is preferably formed by the solvent cast method in the description of the method for producing the transparent support described above. The thickness of the transparent protective film is preferably 10 to 200 μm, more preferably 20 to 100 μm, and still more preferably 60 to 100 μm.

<Polarizing film>
As the polarizing film (polarizer) used in the polarizing plate of the present invention, an iodine polarizing film, a dye polarizing film using a dichroic dye, a polyene polarizing film, or the like can be used. The iodine polarizing film and the dye polarizing film are generally manufactured using a polyvinyl alcohol film.
As a polarizing film, a polarizing film of any manufacturing method can be applied. For example, when a polyvinyl alcohol film is continuously supplied and stretched by applying tension while holding both ends thereof by holding means, the holding means from the substantial holding start point to the substantial holding release point at one end of the film And the locus L2 of the holding means from the substantial holding start point at the other end to the substantial holding release point are in the relationship of the following expression (e) with respect to the distance W between the left and right substantial holding release points, The straight line connecting the substantial holding start points is substantially orthogonal to the center line of the film introduced into the holding process, and the straight line connecting the left and right substantial holding release points is approximately orthogonal to the film center line sent to the next process. It may be stretched as described above (see US Patent Application Publication No. 2002/8840).
| L2-L1 |> 0.4W ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Formula (e)

Since the polarizing film has characteristics such as low mechanical strength and hygroscopicity, it can be protected by disposing a protective film (protective film) on both sides to obtain a polarizing plate.
As the protective film for the polarizing film for the polarizing plate of the present invention, as described above, the optical compensation film of the present invention and cellulose triacetate can be used in pairs.

The angle formed between the slow axis of the transparent protective film used in the polarizing plate of the present invention and the transmission axis of the polarizing film is preferably 3 ° or less, and preferably 2 ° or less. More preferably, it is more preferable to arrange it at 1 ° or less.
As the protective film paired with the optical compensation film, a base film with a hard coat layer, a film with a functional thin film, and the like can be used in combination. For example, it is also preferable that the outermost surface is provided with an antireflection film having antifouling properties and scratch resistance. Any conventionally known antireflection film can be used.

  In particular, an antireflection film is preferably provided on the air side surface of the transparent protective film. The air side surface is a surface on the opposite side of the surface using the cellulose acylate optical compensation film of the present invention as a transparent protective film of the polarizing film, and refers to a surface on the viewing side. Thereby, the drawn image of the liquid crystal display device is preferable because a clear image without reflection of external light and glare is obtained.

[Antireflection film]
The antireflection film is preferably formed by providing a low refractive index layer which is also an antifouling layer on a transparent support, and is composed of a low refractive index layer and at least one layer having a higher refractive index than the low refractive index layer (that is, More preferably, a high refractive index layer, a medium refractive index layer, etc.) are provided on a transparent support.
As a method for forming the antireflection film, a multilayer film obtained by laminating transparent thin films of inorganic compounds (metal oxides, etc.) having different refractive indexes, a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, a metal alkoxide, etc. In the sol-gel method of the metal compound, a method of forming a thin film by post-processing after forming a colloidal metal oxide particle film can be mentioned.
Examples of the post-treatment include ultraviolet irradiation and plasma treatment. For the ultraviolet irradiation, the technique described in JP-A-9-157855 can be used.
For the plasma treatment, the technique described in JP-A-2002-327310 can be used.
Further, as an antireflection film having high productivity, an antireflection film formed by laminating and applying a thin film in which inorganic particles are dispersed in a matrix can be mentioned.
Furthermore, the antireflection film which gave the anti-glare property because the surface of the uppermost layer has a fine uneven shape on the antireflection film by coating as described above is also included.

-Layer structure of coating type antireflection film-
As described above, the antireflection film has at least one layer (high refractive index layer) having a refractive index higher than that of the low refractive index layer on the transparent support, and a layer configuration in the order of the low refractive index layer (outermost layer). It is preferable to become.
In the case where at least one layer having a higher refractive index than the low refractive index layer is made into two layers, the layer structure in the order of the middle refractive index layer, the high refractive index layer, and the low refractive index layer (outermost layer) on the transparent support. Preferably it consists of.
The antireflection film having such a structure has a refractive index satisfying the relationship of “refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer”. Designed to have. The refractive index of each refractive index layer is relative.
Further, a hard coat layer may be provided between the transparent support and the medium refractive index layer. Further, the antireflection film may comprise a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer.
Examples of the antireflection film include those described in JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-11706, and the like. Things.
Other functions may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (eg, JP-A-10-206603, JP-A-2002). -243906 publication etc.) etc. are mentioned.
The haze value of the antireflection film is preferably 5% or less, more preferably 3% or less. Further, the strength of the antireflection film is preferably H or more, more preferably 2H or more, and further preferably 3H or more in a pencil hardness test according to JIS K5400.

-Transparent support used for antireflection film-
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.
The haze value of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. Furthermore, the refractive index of the transparent support is preferably 1.4 to 1.7.
As the transparent support, it is preferable to use a plastic film. Examples of plastic film materials include cellulose acylate, polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl. Examples include methacrylate and polyether ketone. Among these, when an antireflection film is provided on the polarizing plate, a cellulose acylate film is preferable.

--High refractive index layer and medium refractive index layer--
The layer having a high refractive index of the antireflective film is preferably composed of a curable film containing ultrafine particles of high refractive index having an average particle diameter of 100 nm or less and a matrix binder.
Examples of the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1.9 or more. Examples thereof include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms.
Particularly preferred are inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from Co, Zr, and AL (hereinafter sometimes referred to as “specific oxide”), and particularly preferred elements. Is Co.
The total content of Co, Al, and Zr with respect to Ti is preferably 0.05 to 30% by mass, more preferably 0.1 to 10% by mass, and 0.2 to 7% by mass with respect to Ti. More preferably, 0.3-5 mass% is especially preferable, and 0.5-3 mass% is the most preferable.
Co, Al, and Zr are present inside and on the surface of inorganic fine particles mainly composed of titanium dioxide. More preferably, Co, Al, and Zr are present inside the inorganic fine particles mainly composed of titanium dioxide, and most preferably present both inside and on the surface. These specific metal elements may exist as oxides.
Further, as another preferable inorganic particle, a composite oxide of titanium element and at least one metal element (hereinafter also abbreviated as “Met”) selected from metal elements whose oxide has a refractive index of 1.95 or more is used. The composite oxide is composed of inorganic fine particles doped with at least one metal ion selected from Co ions, Zr ions, and Al ions (sometimes referred to as “specific complex oxide”). Can be mentioned.
Here, Ta, Zr, In, Nd, Sb, Sn, and Bi are preferable as the metal element of the metal oxide having a refractive index of 1.95 or more, and Ta, Zr, Sn, and Bi are preferable. Is particularly preferred.
The content of the metal ions doped in the composite oxide is preferably from the viewpoint of maintaining the refractive index, in a range not exceeding 25 mass% with respect to the total amount of metal [Ti + Met] constituting the composite oxide, 0.05-10 mass% is more preferable, 0.1-5 mass% is still more preferable, and 0.3-3 mass% is the most preferable.
The doped metal ion may exist as either a metal ion or a metal atom, and preferably exists appropriately from the surface to the inside of the composite oxide. More preferably, it exists both on the surface and inside.

Examples of the ultrafine particles as described above include a method of treating the particle surface with a surface treatment agent, a method of forming a core-shell structure with a high refractive index particle as a core, and a method of using a specific dispersant in combination. .
Examples of the surface treatment agent exemplified in the method of treating the particle surface with the surface treatment agent include silanes described in JP-A Nos. 11-295503, 11-153703, and 2000-9908. An anionic compound or an organometallic coupling agent described in JP-A No. 2001-310432 and the like is disclosed.
As a method for forming a core-shell structure with high refractive index particles as a core, techniques described in JP-A No. 2001-166104, US Patent Publication No. 2003/0202137, and the like can be used.
Further, examples of a method of using a specific dispersant in combination include techniques described in JP-A No. 11-153703, US Pat. No. 6,210,858 and JP-A No. 2002-27776069.

Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films.
Furthermore, the composition is selected from a polyfunctional compound-containing composition containing at least two radically polymerizable and / or cationic polymerizable groups, an organometallic compound containing a hydrolyzable group, and a partial condensate composition thereof. At least one composition is preferred. Examples thereof include compounds described in JP-A 2000-47004, JP-A 2001-315242, JP-A 2001-31871, JP-A 2001-296401, and the like.
Also preferred are curable films obtained from colloidal metal oxides obtained from hydrolyzed condensates of metal alkoxides and metal alkoxide compositions. Examples thereof include those described in JP-A-2001-293818.
The refractive index of the high refractive index layer is preferably 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm.
The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70. The thickness of the medium refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm.

--- Low refractive index layer--
It is preferable that the low refractive index layer is sequentially laminated on the high refractive index layer. The refractive index of the low refractive index layer is preferably 1.20 to 1.55, more preferably 1.30 to 1.50.
The low refractive index layer is preferably constructed as an outermost layer having scratch resistance and antifouling properties. As means for greatly improving the scratch resistance, imparting slipperiness to the surface is effective, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.

The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50, and more preferably 1.36 to 1.47. The fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing fluorine atoms in a range of 35 to 80% by mass.
For example, paragraph numbers [0018] to [0026] in the specification of JP-A-9-222503, paragraph numbers [0019] to [0030] in the specification of JP-A-11-38202, and JP-A-2001-40284. Examples thereof include compounds described in paragraph numbers [0027] to [0028] of the specification of the publication, JP-A 2000-284102, and JP-A 2004-45462.
The silicone compound is a compound having a polysiloxane structure, and preferably contains a curable functional group or a polymerizable functional group in the polymer chain and has a crosslinked structure in the film. For example, reactive silicone (eg, Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane (Japanese Patent Laid-Open No. 11-258403, etc.) and the like can be mentioned.

  The crosslinking or polymerization reaction of the fluorine-containing and / or siloxane polymer having a crosslinking or polymerizable group is performed simultaneously with or after the application of the coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like. It is preferable to carry out by light irradiation or heating. A conventionally well-known thing can be used as a polymerization initiator and a sensitizer.

Also preferred is a sol-gel cured film in which an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (JP 58-142958, JP 58-147483, JP 58-147484, JP 9-157582). Compounds described in JP-A-11-106704, etc.), silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (JP-A No. 2000-117902, JP-A No. 2001-48590) And the compounds described in JP-A-2002-53804).
The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as a filler (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as an additive other than the above. It is preferable to contain a low refractive index inorganic compound.
In particular, it is preferable to use hollow inorganic fine particles in order to further reduce the increase in the refractive index of the low refractive index layer.
The refractive index of the hollow inorganic fine particles is preferably 1.17 to 1.40, more preferably 1.17 to 1.37, and still more preferably 1.17 to 1.35. The refractive index here represents the refractive index of the whole particle, and does not represent the refractive index of only the outer shell forming the hollow inorganic fine particles.
At this time, assuming that the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity w (%) represented by the following formula (f) is calculated as follows.

^{w = (4πa 3/3)} / (4πb 3/3) × 100 ·········· formula (f)

The porosity is preferably 10 to 60%, more preferably 20 to 60%, and still more preferably 30 to 60%. The refractive index of the hollow particles is preferably 1.17 or more from the viewpoint of the strength of the particles and the scratch resistance of the low refractive index layer containing the hollow particles.
The average particle diameter of the hollow inorganic fine particles in the low refractive index layer is preferably 30% or more and 100% or less of the thickness of the low refractive index layer, and 35% or more and 80% of the thickness of the low refractive index layer. % Or less, more preferably 40% or more and 60% or less of the thickness of the low refractive index layer.
That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the inorganic fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
The refractive index of these hollow inorganic fine particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  As other additives, organic fine particles described in paragraphs [0020] to [0038] of JP-A No. 11-3820, silane coupling agents, slip agents, surfactants, and the like can be contained.

When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.).
The coating method is preferable because it can be manufactured at a low cost.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and still more preferably 60 to 120 nm.

-Other layers of antireflection film-
The antireflection film may further be provided with a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like.

-Hard coat layer-
The hard coat layer can impart physical strength to the antireflection film and is preferably provided on the surface of the transparent support. In particular, it is preferable to provide a hard coat layer between the transparent support and the high refractive index layer.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound.
The curable functional group is preferably a photopolymerizable functional group, or the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound.
Specific examples of these compounds are the same as those exemplified for the high refractive index layer.
Specific examples of the constituent composition of the hard coat layer include those described in JP-A No. 2002-144913, JP-A No. 2000-9908, International Publication No. WO00 / 46617, and the like.
The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable to form fine particles dispersed in the hard coat layer using the method described for the high refractive index layer.

The hard coat layer can also serve as an antiglare layer containing particles having an average particle size of 0.2 to 10 μm and imparting an antiglare function (antiglare function (described later)).
There is no restriction | limiting in particular in the film thickness of a hard-coat layer, According to the objective, it can select suitably, For example, it is preferable that it is 0.2-10 micrometers, and it is more preferable that it is 0.5-7 micrometers.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and still more preferably 3H or higher, in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

-Forward scattering layer-
When applied to a liquid crystal display device, the forward scattering layer is preferable because it can provide a viewing angle improvement effect when the viewing angle is inclined in the vertical and horizontal directions. By dispersing fine particles having different refractive indexes in the hard coat layer, it can also serve as a hard coat function.
As the forward scattering layer, for example, Japanese Patent Application Laid-Open No. 11-38208 in which the forward scattering coefficient is specified, Japanese Patent Application Laid-Open No. 2000-199809 in which the relative refractive index of the transparent resin and the fine particles is in a specific range, and a haze value of 40% or more. The thing as described in Unexamined-Japanese-Patent No. 2002-107512 etc. which prescribed | regulated.

[Formation of antireflection film]
Each layer of the antireflection film is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating, a micro gravure method or an extrusion coating method (US Pat. No. 2,681,294). It can be formed by coating.

-Anti-glare function-
The antireflection film may have an antiglare function that scatters external light. The antiglare function is obtained by forming irregularities on the surface of the antireflection film. When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 50%, more preferably 5 to 30%, and further preferably 5 to 20%.

As a method for forming irregularities on the surface of the antireflection film, any method can be applied as long as these surface shapes can be sufficiently maintained.
For example, a method of forming irregularities on the film surface using fine particles in the low refractive index layer (for example, JP 2000-271878 A), a lower layer of the low refractive index layer (high refractive index layer, medium refractive index layer) Alternatively, a relatively large particle (particle size 0.05 to 2 μm) is added to a hard coat layer in a small amount (0.1 to 50% by mass) to form a surface uneven film, and these shapes are maintained on it. A method of providing a low refractive index layer (for example, JP-A No. 2000-281410, JP-A No. 2000-95893, JP-A No. 2001-100004, JP-A No. 2001-281407, etc.), uppermost layer (antifouling property) A method of physically transferring the uneven shape onto the surface after coating the layer (for example, as an embossing method, JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401) etc Mounting) and the like.

In the polarizing plate provided with the antireflection film of the present invention, it is preferable that the transparent support provided with the antireflection film also serves as a protective film for the polarizing plate.
Here, the surface of the cellulose acylate film opposite to the side provided with the antireflection film of the transparent support (preferably the cellulose acylate film) is hydrophilized, and is prepared by bonding the polarizing film and the adhesive together. It is preferable to do.
Examples of the hydrophilization treatment include those similar to the above-mentioned [surface treatment of optical compensation film].
As described above, the optical compensation film of the present invention is used as a film also serving as a protective film on the surface opposite to the antireflection film of the polarizing film, as described above.
Here, the provision of the optically anisotropic layer of the transparent support of the optical compensation film is preferably produced by hydrophilizing the surface on the opposite side and bonding the polarizing film and the adhesive together.
Thereby, the thickness of the polarizing plate is reduced, and the weight of the liquid crystal display device can be reduced, which is preferable.

(Liquid crystal display device)
The liquid crystal display device of the present invention comprises a liquid crystal cell and two polarizing plates arranged on both sides thereof. The liquid crystal cell carries a liquid crystal between two electrode substrates.
One optical compensation film is disposed between the liquid crystal cell and one polarizing plate, or two optical compensation films are disposed between the liquid crystal cell and both polarizing plates.

As an example of the liquid crystal display device of the present invention, the structure of an OCB mode liquid crystal display device is shown in FIG. As shown in FIG. 1, the liquid crystal display device of the present invention includes a liquid crystal layer 7 in which liquid crystal is bend-oriented with respect to the substrate surface when a voltage is applied, that is, black display, and a liquid crystal composed of a substrate 6 and a substrate 8 sandwiching the liquid crystal layer. Cell.
As for the board | substrate 6 and the board | substrate 8, the alignment process is given to the surface at the side of a liquid crystal layer. The orientation direction (rubbing direction) is indicated by an arrow RD. In the case of the back surface, it is indicated by a broken line arrow. The polarizing films 1 and 101 are disposed so as to sandwich the liquid crystal cell, and the transmission axis 2 of the polarizing film 1 and the transmission axis 102 of the polarizing film 101 are orthogonal to each other and in the RD direction of the liquid crystal layer of the liquid crystal cell. And 45 ° with respect to each other.
An optical compensation film 13A (113A) is disposed between the polarizing film 1 (101) and the liquid crystal cell. The optical compensation film 13a (113a) is composed of a cellulose acylate film 13a (113a) and a discotic compound. The optically anisotropic layer 5 (9) is fixed in a hybrid alignment state in which the inclination angle with respect to the film plane is different in the thickness direction. The cellulose acylate film 13a (113a) has a slow axis 4a (104a) arranged in parallel with the direction of the transmission axis 2 (102) of the polarizing film 1 (101) adjacent thereto.

The liquid crystal cell in FIG. 1 includes a liquid crystal layer formed of an upper substrate 6 and a lower substrate 8 and liquid crystal molecules 7 sandwiched therebetween. An alignment film (not shown) is formed on the surface of the substrate 6 and the substrate 8 that is in contact with the liquid crystal molecules 7 (hereinafter sometimes referred to as “inner surface”). The orientation of the molecules 7 is controlled in a parallel direction with a pretilt angle.
Further, on the inner surfaces of the substrate 6 and the substrate 8, a transparent electrode (not shown) capable of applying a voltage to the liquid crystal layer made of the liquid crystal molecules 7 is formed.
In the present invention, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn is preferably 0.1 to 1.5 μm, more preferably 0.2 to 1.5 μm. Is more preferably 0.2 to 1.2 μm, and particularly preferably 0.6 to 0.9 μm. In these ranges, since the white display luminance when white voltage is applied is high, a bright and high-contrast display device can be obtained.
The liquid crystal material to be used is not particularly limited, but in a mode in which an electric field is applied between the upper and lower substrates 6 and 8, a liquid crystal having a positive dielectric anisotropy such that the liquid crystal molecules 7 respond in parallel to the electric field direction. Use materials.

For example, when the liquid crystal cell is an OCB mode liquid crystal cell, a nematic having a positive dielectric anisotropy between Δn = 0.08 and Δε = 5 between the upper substrate 6 and the lower substrate 8. A liquid crystal material or the like can be used.
The thickness d of the liquid crystal layer is not particularly limited, but can be set to about 4 μm when the liquid crystal having the above characteristics is used. The brightness at the time of white display changes depending on the thickness Δ and the product Δn · d of the refractive index anisotropy Δn when white voltage is applied, so that sufficient brightness can be obtained when white voltage is applied. In this case, Δn · d of the liquid crystal layer in the non-application state is preferably set to be in the range of 0.6 to 1.5 μm.

In addition, in the OCB mode liquid crystal display device, the addition of a chiral agent generally used in the TN mode liquid crystal display device is rarely used because it deteriorates the dynamic response characteristics, but in order to reduce alignment defects. May be added.
In addition, the multi-domain structure is advantageous for adjusting the alignment of the liquid crystal molecules in the boundary region between the domains.
Here, the multi-domain structure refers to a structure in which one pixel of a liquid crystal display device is divided into a plurality of regions. For example, in the OCB mode, a multi-domain structure is preferable because the viewing angle characteristics of luminance and color tone are improved.
Specifically, each pixel is composed of two or more (preferably 4 or 8) regions in which the initial alignment state of the liquid crystal molecules is different from each other, and averaging is performed. Can be reduced.
Further, the same effect can be obtained even if each pixel is constituted by two or more different regions where the alignment direction of liquid crystal molecules continuously changes in a voltage application state.

The transparent support 13a (113a) may function as a support for the optically anisotropic layer 5 (9), may function as a protective film for the polarizing film 1 (101), It may have both functions. That is, the polarizing film 1 (101), the transparent support 13a (113a), and the optically anisotropic layer 5 (9) may be incorporated into the liquid crystal display device as an integrated laminate, Each may be incorporated as a single member.
Further, a protective film for a polarizing film may be separately disposed between the transparent support 13a (113a) and the polarizing film 1 (101), but the protective film is not disposed. Is preferred. The slow axis 14a of the transparent support 13a and the slow axis 114a of the transparent support 113a are preferably substantially parallel or orthogonal to each other.
When the slow axis 14a of the transparent support 13a and the slow axis 114a of the transparent support 113a are orthogonal to each other, the birefringence of the respective transparent supports is mutually canceled, so that the liquid crystal display device is perpendicularly incident. It is possible to reduce deterioration of optical characteristics of light.
Further, in a mode in which the slow axes 14a and 114a are parallel to each other, when there is a residual phase difference in the liquid crystal layer, the phase difference can be compensated by birefringence of the protective film.

  Regarding the transmission axis 2 (102) of the polarizing film 1 (101), the slow axis direction 14a (114a) of the transparent support 13a (113a), and the alignment direction of the liquid crystal molecules 7, the materials used for each member and the display mode Then, the optimum range is adjusted according to the laminated structure of the members. That is, the transmission axis 2 of the polarizing film 1 and the transmission axis 102 of the polarizing film 101 are arranged so as to be substantially orthogonal to each other. However, the liquid crystal display device of the present invention is not limited to this configuration.

The optically anisotropic layer 5 (9) is disposed between the transparent support 13a (113a) and the liquid crystal cell. The optically anisotropic layer 5 (9) is a layer formed from a composition containing a liquid crystal compound, for example, a rod-like compound or a discotic compound.
In the optically anisotropic layer 5 (9), the molecules of the liquid crystalline compound are fixed in a predetermined alignment state.
The orientation average direction 5a (9a) at least at the interface of the transparent support 13a (113a) of the molecular symmetry axis of the liquid crystalline compound in the optically anisotropic layer 5 (9) and the in-plane of the transparent support 13a (113a) Intersects with the slow axis 14a (114a) of approximately 45 °. When arranged in such a relationship, the optically anisotropic layer 5 (9) causes retardation with respect to the incident light from the normal direction, does not cause light leakage, and incident light from the oblique direction. In contrast, the effects of the present invention can be sufficiently achieved.
Also at the interface on the liquid crystal cell side, the orientation average direction of the molecular symmetry axis of the optically anisotropic layer 5 (9) is relative to the slow axis 14a (114a) in the plane of the transparent support 13a (113a). It is preferable to make approximately 45 °.

In addition, the orientation average direction 5a on the polarizing film side (optical anisotropic layer interface side) of the molecular symmetry axis of the liquid crystalline compound of the optically anisotropic layer 5 is substantially the same as the transmission axis 2 of the polarizing film 1 located closer. It is preferable to arrange at 45 °.
Similarly, the alignment average direction 9a on the polarizing film side (optical anisotropic layer interface side) of the molecular symmetry axis of the liquid crystalline compound of the optically anisotropic layer 9 is closer to the transmission axis 102 of the polarizing film 101 positioned closer to the optical axis. It is preferable to arrange at approximately 45 °. When arranged in such a relationship, optical switching can be performed according to the sum of the retardation generated in the optically anisotropic layer 5 (9) and the retardation generated in the liquid crystal layer, and incident light from an oblique direction. In contrast, the effects of the present invention can be sufficiently achieved.

  The liquid crystal display device of the present invention can be used in a normally white mode in which a bright display is applied when the applied voltage is low and a dark display is displayed when the applied voltage is high, a dark display is displayed when the applied voltage is low, and a normally black mode is displayed when the applied voltage is high. it can.

The driving method of the transmissive, reflective, and transflective liquid crystal display devices of the present invention is preferably an active matrix method rather than a simple matrix method, and is a thin film transistor (TFT), a thin film diode (TFD), or an MIM (Metal Metal). It is more preferable to use Insulator Metal). It is more preferable to use low-temperature polysilicon or continuous grain boundary silicon for the TFT.
For details, see “Liquid Crystal Device Handbook”, Japan Society for the Promotion of Science 142nd Committee, Nikkan Kogyo Shimbun, “Liquid Crystal Application”, Okano Koji, Bafukan, “Color LCD,” Shunsuke Kobayashi, etc. “Liquid Crystal Display Technology”, Tatsuo Uchida, Industrial Research Committee, “Leading Edge of Liquid Crystal Display”, Liquid Crystal Young Research Group, Sigma Publishing, “Liquid Crystal: Fundamentals and New Applications of LCD” Liquid Crystal Young Research Group, Sigma Publishing, etc. Yes.

  In the liquid crystal display device of the present invention, for example, TN mode, STN mode, ECB mode, and the like, and as the ECB mode, liquid crystal cells of various modes such as OCB mode, HAN mode, VA mode, MVA mode, and homogeneous alignment mode are used. However, TN mode and ECB mode liquid crystal cells such as OCB mode, HAN mode, VA mode, MVA mode, and homogeneous alignment mode are particularly preferable. Regarding liquid crystal cells, “'99 PDP / LCD component materials and chemicals market” July 30, 1999, CM, “EL, PDP, LCD display technology and latest trends in the market”, March 2001, Toray Research Center Etc. are described.

  A preferred form of the optically anisotropic layer in each liquid crystal mode will be described below.

<TN mode liquid crystal display device>
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents. The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

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

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

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

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.

[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ 100 parts by mass ・ m-hydroxybenzoic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・··· 10 parts by mass · Methylene chloride (first solvent) ··················· 633 parts by mass · Methanol (second solvent) ··· ... 95 parts by mass
-Retardation control agent shown in the following structural formula (A): 6.5 parts by mass

  The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes. The residual solvent amount after drying was 20% by mass. The obtained cellulose acetate film was peeled from the glass plate and dried at 100 ° C. for 10 minutes and 140 ° C. for 20 minutes. The dried film was uniaxially stretched to 130% at a temperature of 175 ° C. to produce a support. The film thickness of the produced film was 80 μm.

<Measurement of Re and Rth>
As the optical characteristics after conditioning the prepared transparent support in an environment of 25 ° C., 10% RH, and 80% RH for 2 hours, Re and Rth of the support at wavelengths of 450 nm, 550 nm, and 630 nm were set as follows. According to the method described above, measurement was performed with KOBRA 21ADH (manufactured by Oji Scientific Instruments). The measurement results are shown in Table 3.

(Example 2)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.

[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass ・ Methylene disalicylic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・··· 10 parts by mass · Methylene chloride (first solvent) ················ 633 parts by mass · Methanol (second solvent) ···・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 95 parts by mass
-Retardation control agent shown in the structural formula (A)-6.5 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes. The residual solvent amount after drying was 20% by mass.
The obtained cellulose acetate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 130% at a temperature of 175 ° C. to prepare a support. The film thickness of the produced film was 80 μm.

Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.
In addition, methylene disalicylic acid had a higher molecular weight than m-hydroxybenzoic acid described in Example 1, and was able to suppress volatility during film drying.

(Example 3)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.

[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ 100 parts by mass ・ Methylene disalicylic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ ・ 10 parts by mass ・ Methylene chloride (first solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 612 parts by mass ・ Methanol (second solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・... 91 parts by mass
-Retardation control agent shown in structural formula (B) below: 2.5 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes. The residual solvent amount after drying was 20% by mass.
The obtained cellulose acetate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 160% at a temperature of 180 ° C. to prepare a support. Thickness of the produced film was 80 [mu] m.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.
( Reference Example 4)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.

[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ 100 parts by mass ・ Methylene disalicylic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 10 parts by mass · Methylene chloride (first solvent) ········· 625 parts by mass · Methanol (second solvent) ··· ... 93 parts by mass
-Retardation control agent shown in structural formula (C) below: 5.0 parts by mass

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 5)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.

[Material / solvent composition]
・ Cellulose acetate (Substitution degree: 2.71) ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass ・ Methylene disalicylic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 10 parts by mass · Methylene chloride (first solvent) · · · · · · 604 parts by mass · Methanol (second solvent) · · · .... 90 parts by mass
-Retardation control agent shown in the structural formula (B)-1.0 mass part

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 6)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.

[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.94) ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass ・ Methylene disalicylic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・... 10 parts by mass · Methylene chloride (first solvent) ················ 653 parts by mass · Methanol (second solvent) ... ... 98 parts by mass
-Retardation control agent shown in the above structural formula (B) ... 10 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes. The residual solvent amount after drying was 20% by mass.
The obtained cellulose acetate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 160% at a temperature of 200 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 7)
<Preparation of transparent support>
A cellulose triacetate (triacetyl cellulose: TAC) solution was prepared in the same manner as in Example 3, except that the additive represented by the following structural formula (D) was used instead of methylene disalicylic acid in Example 3.

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 8)
<Preparation of transparent support>
A cellulose triacetate (triacetyl cellulose: TAC) solution was prepared in the same manner as in Example 3 except that the additive shown in the following structural formula (E) was used instead of methylene disalicylic acid in Example 3.

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

( Reference Example 9)
<Preparation of transparent support>
A cellulose triacetate (triacetyl cellulose: TAC) solution was prepared in the same manner as in Example 3 except that benzoic acid was used instead of methylene disalicylic acid in Example 3.

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 10)
<Preparation of transparent support>
Instead of the retardation control agent shown in Structural Formula (B) in Example 3, an additive shown in Structural Formula (F) below was used, and m-hydroxybenzoic acid was used instead of methylene disalicylic acid in Example 3. A cellulose triacetate (triacetylcellulose: TAC) solution was prepared in the same manner as in Example 3 except that it was used.

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 11)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose propionate (acetyl substitution degree 1.89 propionyl substitution degree 0.68) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ 100 parts by mass ・ m-hydroxybenzoic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 11 parts by mass ・ Methylene chloride (first solvent) ・ ・ ・ ・ ・ ・398 mass parts, methanol (second solvent), 54 mass parts
-Retardation control agent shown in the structural formula (B) ... 2.0 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes.
The obtained cellulose propionate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 130% at a temperature of 130 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 12)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose propionate (acetyl substitution degree 1.54, propionyl substitution degree 0.84) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ 100 mass parts ・ m-hydroxybenzoic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 13 mass parts ・ Methylene chloride (first solvent) ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 405 parts by mass ・ Methanol (second solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 55 parts by mass
-Retardation control agent shown in the structural formula (B)-2.0 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes.
The obtained cellulose propionate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 130% at a temperature of 130 ° C. to prepare a support. The film thickness of the produced film was 40μ.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 13)
<Preparation of transparent support>
Cellulose triacetate (triacetyl cellulose: triacetyl cellulose: in the same manner as in Example 3 except that the additive shown in the following structural formula (G) was used instead of the retardation control agent shown in the structural formula (B) in Example 3. TAC) solution was prepared.

The obtained dope was stretched after drying under the same conditions as in Example 3. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 14)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass ・ m-hydroxybenzoic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・··· 10 parts by mass · Methylene chloride (first solvent) · · · · · · 609 parts by mass · Methanol (second solvent) ············· 91 parts by mass · Retardation control agent shown in the above structural formula (B) ········ 1.0 parts by mass
-Retardation control agent shown in structural formula (H) below: 1.0 part by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes.
The residual solvent amount after drying was 20% by mass. The obtained cellulose acetate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 160% at a temperature of 180 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Example 15)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose propionate (acetyl substitution degree 1.89 propionyl substitution degree 0.68) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ 100 mass parts ・ m-hydroxybenzoic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 11 mass parts ・ methylene chloride (first solvent) ・ ・ ・ ・ ・ ・............ 392 parts by massMethanol (second solvent) ... 54 parts by mass
-Retardation control agent shown in the structural formula (B)-0.5 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes.
The obtained cellulose propionate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 130% at a temperature of 130 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Comparative Example 1)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass ・ Triphenyl phosphate (plasticizer) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6 .5 parts by mass-biphenyl diphenyl phosphate (plasticizer) ... 5.2 parts by mass-methylene chloride (first solvent) ...・ ・ ・ 643 parts by mass ・ Methanol (second solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 96 parts by mass
-Retardation control agent shown in the above structural formula (A) ... 6.5 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes. The residual solvent amount after drying was 20% by mass.
The obtained cellulose acetate film was peeled from the glass plate and dried at 100 ° C. for 10 minutes and 140 ° C. for 20 minutes.
The dried film was uniaxially stretched to 120% at a temperature of 155 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Comparative Example 2)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose acetate (substitution degree 2.81) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 100 parts by mass ・ m-hydroxybenzoic acid ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ ・ ・ 10 parts by mass ・ Methylene chloride (first solvent) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 598 parts by mass
-Methanol (second solvent) ... 89 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes. The residual solvent amount after drying was 20% by mass.
The obtained cellulose acetate film was peeled from the glass plate and dried at 100 ° C. for 10 minutes and 140 ° C. for 20 minutes.
The dried film was uniaxially stretched to 130% at a temperature of 130 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

(Comparative Example 3)
<Preparation of transparent support>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose triacetate (triacetyl cellulose: TAC) solution.
[Material / solvent composition]
・ Cellulose propionate (acetyl substitution degree 1.89 propionyl substitution degree 0.68) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・· 100 parts by mass · Compound shown in the following structural formula (I) · · · · · · · 5 parts by mass · Compound shown in the following structural formula (J) · · ····················· 5 parts by mass · Methylene chloride (first solvent) ······················· Parts · Methanol (second solvent) ·············· 54 parts by weight · Tinuvin 109 (Ciba Specialty Chemicals Co., Ltd.) ··· 1.2 parts by mass Tinuvin 171 (Ciba Specialty Chemicals Co., Ltd.) 0.5 parts by mass Silicon oxide fine particles (Aerosil R) 972V ( manufactured by Nippon Aerosil Co., Ltd.)) ... 0.1 parts by mass

The obtained dope was cast on a glass plate, dried at room temperature for 1 minute, and then dried at 70 ° C. for 6 minutes.
The obtained cellulose propionate film was peeled from the glass plate and dried at 140 ° C. for 30 minutes.
The dried film was uniaxially stretched to 130% at a temperature of 130 ° C. to prepare a support. The film thickness of the produced film was 80 μm.
Further, Re and Rth were measured in the same manner as in Example 1. The measurement results are shown in Table 3.

<Saponification treatment>
On the band surface side of the transparent supports prepared in Examples 1 to 3, 5 to 8, 10 to 15, Reference Examples 4 and 9, and Comparative Examples 1 to 3, a 1.0 N potassium hydroxide solution (solvent: water / (Isopropyl alcohol / propylene glycol = 69.2 parts by mass / 15 parts by mass / 15.8 parts by mass) was applied at 10 mL / m ² and kept at a temperature of about 40 ° C. for 30 seconds. After washing with water, water drops were removed with an air knife. Then, it dried at 100 degreeC for 15 second.

<Preparation of alignment film>
On the transparent supports prepared in Examples 1 to 3, 5 to 8 , 10 to 13, Reference Examples 4 and 9, and Comparative Examples 1 to 2, an alignment film coating solution having the following composition was used with a # 16 wire bar coater. 28 mL / m ^{2 was} applied. The film was dried with warm air of 60 ° C. for 60 seconds and further with warm air of 90 ° C. for 150 seconds to produce an alignment film.

[Alignment film coating solution composition]
・ Modified polyvinyl alcohol represented by the following structural formula (K): 10 parts by mass, water: ... 371 parts by mass, methanol ... 119 parts by mass, glutaraldehyde (crosslinking agent) ... 0.5 parts by mass
・ Citrate ester (AS3 manufactured by Sankyo Chemical Co., Ltd.) ... 0.35 parts by mass

Drying was performed at 25 ° C. for 60 seconds, 60 ° C. warm air for 60 seconds, and 90 ° C. warm air for 150 seconds.
The thickness of the alignment film after drying was 1.1 μm.
The surface roughness of the alignment film was 1.147 nm as measured with an atomic force microscope (AFM: Atomic Force Microscope, SPI3800N, manufactured by Seiko Instruments Inc.).

<Formation of optically anisotropic layer>
In 400.0 parts by mass of methyl ethyl ketone, 100 parts by mass of a discotic liquid crystal compound represented by the following structural formula (L), 0.4 parts by mass of an air interface alignment controller represented by the following structural formula (M), a photopolymerization initiator ( A coating solution was prepared by dissolving 3 parts by mass of Irgacure 907 (manufactured by Ciba Geigy) and 1 part by mass of a sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.).
The coating solution was applied onto the alignment film with a # 2.0 wire bar. This was attached to a metal frame and heated in a constant temperature bath at 120 ° C. for 90 seconds to align the discotic liquid crystal compound.
Next, using a 120 W / cm high-pressure mercury lamp at 80 ° C., ultraviolet rays were irradiated for 1 minute to polymerize the discotic liquid crystal compound. Then, it stood to cool to room temperature.
In this way, an optically anisotropic layer was formed on the support via an alignment film to produce an optical compensation film.

<Measurement of optical properties of optically anisotropic layer>
An alignment film was produced on glass in the same manner as described above, the optically anisotropic layer was formed on the alignment film, and Re (550) was measured with light having a wavelength of 550 nm using an ellipsometer M-150. However, it was 30 nm.
Further, when the retardation ratio was measured with an ellipsometer M-150 using light having a wavelength of 450 nm and light of 650 nm, Re (450) / Re (650) was 1.15. Moreover, it was 0.8 micrometer when the thickness of the optically anisotropic layer was measured.

The discotic liquid crystal compound represented by the structural formula (H) was poured into a 2 μm glass cell in which the director of the discotic liquid crystal compound was aligned in parallel in the plane while being heated, and left for 2 minutes.
When the retardation value Re_m (550) of this cell was measured using an ellipsometer M-150 with light having a wavelength of 550 nm, it was 235 nm. Since the cell gap was 2 μm, the value of Re_m (550) / d was 0.118.

(Preparation of polarizing plate)
First, iodine was adsorbed on a stretched polyvinyl alcohol film to prepare a polarizing film.
Thereafter, an optical compensation film coated with an optically anisotropic layer on the transparent support produced in Examples 1 to 3, 5 to 8, 10 to 13, Reference Examples 4 and 9 , and Comparative Examples 1 to 2, and saponification. The transparent supports prepared in Examples 14 and 15 and Comparative Example 3 after the treatment were attached to one surface of the polarizing film using a polyvinyl alcohol-based adhesive, and the other surface of the polarizing film was applied to the other surface. A commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Film Co., Ltd.) subjected to saponification treatment was attached using a polyvinyl alcohol-based adhesive. Thus, 18 types of polarizing plates based on Examples 1 to 3, 5 to 8, 10 to 15, Reference Examples 4 and 9 and Comparative Examples 1 to 3 were produced.

<Mounting evaluation with liquid crystal display devices>
<Production of bend alignment liquid crystal cell>
A polyimide film was provided as an alignment film on a glass substrate with an ITO electrode, and the alignment film was rubbed. The obtained two glass substrates were faced to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 4.7 μm. A bend-aligned liquid crystal cell was prepared by injecting a liquid crystal compound (ZLI1132, manufactured by Merck & Co., Inc.) having a Δn of 0.1396 into the cell gap.
Prepared in Examples 1 to 3, 5 to 8, 10 to 13, Reference Examples 4 and 9 , and Comparative Examples 1 to 2 on the upper and lower polarizing plates of the liquid crystal display device using the bend alignment type liquid crystal cell. The polarizing plates prepared using the optical compensation film were attached to the observer side and the backlight side one by one through an adhesive so that the optical compensation film was on the liquid crystal cell side. The optically anisotropic layer of the polarizing plate faced the cell substrate, and the rubbing direction of the liquid crystal cell and the rubbing direction of the optically anisotropic layer facing it were antiparallel. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction.
A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. A normally white mode of 2V white display and 5V black display was set. A voltage at which the transmittance at the front surface is minimized, that is, a black voltage, is applied, and a color shift Δx between the azimuth angle 135 ° polar angle 60 ° and the azimuth angle 315 ° polar angle 60 ° is obtained, and based on the following evaluation criteria The color shift was evaluated. The evaluation results are shown in Table 4.
In Table 4 below, “color shift” means ΔCu′v ′: u′v ′ (polar angle 60 °) −u′v ′ (polar angle 0 °) and azimuth angle 315 at an azimuth angle of 135 °. ΔCu′v ′ at °: sum of u′v ′ (polar angle 60 °) −u′v ′ (polar angle 0 °). (U'v ': color coordinates in CIELAB space)
Further, using the measuring device (EZ-Contrast 160D, manufactured by ELDIM) as the contrast ratio, the transmittance ratio (white display / black display), the visual field is displayed in eight stages from black display (L1) to white display (L8). The angle was measured and the viewing angle was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 4.
The viewing angle was measured by adjusting the liquid crystal display device at 25 ° C. 10% / 60% / 80% for 1 week.

[Evaluation criteria for color shift]
A: Δx is less than 0.02 ○: Δx is 0.02-0.04
Δ: Δx is 0.04 to 0.06
X: Δx is 0.06 or more

[Evaluation criteria for viewing angle (polar angle range with contrast ratio of 10 or more and no black-side gradation inversion)]
◎: Polar angle of 80 ° or more in top / bottom / left / right ○: Top / bottom / left / right in three directions, polar angle of 80 ° or more Polar angle 80 ° or more

<Preparation of VA alignment liquid crystal cell>
The liquid crystal cell has a cell gap between substrates of 3.6 μm, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Prepared by forming a layer. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

A polarizing plate using the optical compensation films prepared in Examples 14 and 15 and Comparative Example 3 on the upper and lower polarizing plates of the liquid crystal display device using the vertical alignment type liquid crystal cell is used in the polarizing plate. One sheet was attached to the viewer side and the backlight side through an adhesive so that the optical compensation film side was opposed to the liquid crystal cell side. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction.
A rectangular wave voltage of 55 Hz was applied to the liquid crystal cell. A normally black mode with 5 V white display and 0 V black display was set. The color shift Δx between the azimuth angle 135 ° polar angle 60 ° and the azimuth angle 315 ° polar angle 60 ° was determined, and the color shift was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 4.
Further, using the measuring device (EZ-Contrast 160D, manufactured by ELDIM) as the contrast ratio, the transmittance ratio (white display / black display), the visual field is displayed in eight stages from black display (L1) to white display (L8). The angle was measured and the viewing angle was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 4.
The viewing angle was measured by adjusting the liquid crystal display device at 25 ° C. 10% / 60% / 80% for 1 week.

From the results shown in Table 3-4, at least, a compound A having a plurality of hydrogen-bonding groups in one molecule, the at least any of the compounds B which are tables by the general formula (I) ~ (II) The liquid crystal display device using the optical compensation film of Examples 1-3, 5-8, 10-15, and Reference Examples 4 and 9 to be contained is compared with the liquid crystal display device using the optical compensation film of Comparative Examples 1-3. Thus, it was confirmed that the liquid crystal cell can be optically compensated, the contrast can be improved, the color shift depending on the viewing angle direction can be reduced, and the display characteristics do not change with respect to environmental humidity changes.
In particular, the liquid crystal display devices of Examples 14 to 15 that employ VA mode liquid crystal cells were significantly shown to have no change in display characteristics with respect to environmental humidity changes as compared with the liquid crystal display device of Comparative Example 3.

The optical compensation film and the polarizing plate of the present invention optically compensate the liquid crystal cell, can improve the contrast, reduce the color shift depending on the viewing angle direction, and do not change the display characteristics with respect to the environmental humidity change. It can be suitably used for a display device.
The liquid crystal display device of the present invention optically compensates the liquid crystal cell, can improve the contrast, reduce the color shift depending on the viewing angle direction, and does not change the display characteristics with respect to environmental humidity changes. It can be suitably used for personal computer monitors, televisions, liquid crystal projectors, and the like.

FIG. 1 is a schematic diagram illustrating the configuration of the liquid crystal display device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polarizing film 2 Transmission axis 3a Transparent support 4a In-plane slow axis 5 Optically anisotropic layer 5a Orientation average direction 6 of polarizing film side (interface side of support) of molecular symmetry axis of liquid crystalline compound 6 Substrate 7 Liquid crystallinity Molecule 8 Substrate 9 Optically anisotropic layer 9a Orientation average direction 103a on the polarizing film side (interface side of the support) of the molecular symmetry axis of the liquid crystalline compound Transparent support 104a In-plane slow axis 101 Polarizing film 102 Transmission axis

Claims (9)

At least a plurality of hydrogen bonding groups in one molecule, the hydrogen bonding group is a hydroxyl group or a carboxyl group, has 1 to 2 aromatic rings as a mother nucleus, and has a molecular weight of 130 or more and 500 or less. A cellulose acylate containing compound A and compound B represented by at least one of the following general formulas (I) and (II), and satisfying the following formulas (1) to (6): Optical compensation film.
However, in the said general formula (I), R < ¹² > represents the aromatic ring or heterocyclic ring which has a substituent in at least any one of ortho position, meta position, and para position each independently. Moreover, X < ¹¹ > represents a single bond or -NR < ¹³ >-each independently. Wherein, R ¹³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, or an ant Lumpur group.
In the general formula ^{(II), R 4, R} 5, R 6, R 7, R 8, and ^{R 9} represent the same substituent, examples of the substituent include an alkyl group, A reel group, reed Le group , an alkoxycarbonyl group, an aryloxycarbonyl group, mosquitoes Rubamoiru group, sul Honi group, hydrin Rokisamu acid group, hetero b ring group or a silyl group.
10 nm <Re (550) <100 nm (1)
100 nm <Rth (550) <200 nm .......... Formula (2)
0.5 ≦ Re (450) / Re (550) ≦ 1.0 (3)
1.0 ≦ Re (630) / Re (550) ≦ 1.5 (4)
1.0 ≦ Rth (450) / Rth (550) ≦ 1.5 (5)
0.5 ≦ Rth (630) / Rth (550) ≦ 1.0 (6)
In the above formulas (1) to (6), Re (λ) is the retardation value of the optical compensation film with respect to light with a wavelength of λnm, and Rth (λ) is the optical compensation with respect to light with a wavelength of λnm. It is the retardation value in the thickness direction of the film.   The optical compensation film according to claim 1, further comprising an optically anisotropic layer on the optical compensation film and satisfying the above formulas (1) to (6). The optical compensation film according to claim 1, wherein the compound A satisfies the following formula (7).
(Number of hydrogen-bonding groups in one molecule / molecular weight of the compound)> 0.01 ... (7)   The optical compensation film according to any one of claims 1 to 3, wherein the compound B has a ClogP value of 5.1 or more and 15 or less. The optical compensation film according to any one of claims 1 to 4, wherein the cellulose acylate satisfies the following formulas (8) and (9).
2.0 ≦ SA + SB ≦ 3.0 Equation (8)
0 <SB ........... Formula (9)
However, in said Formula (8) and Formula (9), SA is the substitution degree of the acetyl group which has substituted the hydrogen atom of the hydroxyl group of a cellulose, SB substituted the hydrogen atom of the hydroxyl group of a cellulose. The substitution degree of the acyl group having 3 to 22 carbon atoms.   6. The optical compensation film according to claim 2, wherein a discotic compound layer having a hybrid orientation is formed as the optically anisotropic layer.   A polarizing plate comprising the optical compensation film according to claim 1 on at least one side of a polarizing film.   A liquid crystal display device comprising a liquid crystal cell and the polarizing plate according to claim 7. The liquid crystal display device according to claim 8, wherein the liquid crystal cell is an OCB method or a VA method.