JP2006119605A - Optical compensation sheet, manufacturing method thereof, polarizing sheet and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical compensation sheet in which the adhesiveness is reconciled with the satisfactory surface state, its manufacturing method, a polarizing sheet in which the optical compensation sheet is disposed on a half side of a polarizing film, and a liquid crystal display device which is provided with the polarizing sheet and has a high display quality. <P>SOLUTION: In the optical compensation sheet, an alignment film and an optical anisotropic layer made by aligning and polymerizing liquid crystal compounds are laminated in the order on the transparent substrate subjected to adhesiveness imparting treatment beforehand. Therein, the alignment film comprises a layer made by heating and curing an alignment film forming composition which includes an aldehyde compound having two or more aldehyde groups and one or more kinds of nucleophilic agents having nucleophilic constant (n) of 5 to 10. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical compensation sheet having an improved surface shape and a method for producing the optical compensation sheet. Furthermore, the present invention also relates to a polarizing plate using the optical compensation sheet and a liquid crystal display device having the polarizing plate.

A liquid crystal display device is generally composed of a liquid crystal cell, a polarizing plate and an optical compensation sheet (retardation plate), and is roughly classified into a transmission type liquid crystal display device and a reflection type liquid crystal display device.
In a transmissive liquid crystal display device, two polarizing plates are attached to both sides of a liquid crystal cell, and one or two optical compensation sheets are disposed between the liquid crystal cell and the polarizing plate. In a reflective liquid crystal display device, a reflector, a liquid crystal cell, one optical compensation sheet, and one polarizing plate are arranged in this order.
A liquid crystal cell usually comprises a rod-like liquid crystalline molecule, two substrates for enclosing it, and an electrode layer for applying a voltage to the rod-like liquid crystal molecule. Various display modes have been proposed for liquid crystal cells depending on the alignment state of rod-like liquid crystalline molecules. For transmission types, TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), For reflective types such as OCB (Optically Compensatory Bend), STN (Supper Twisted Nematic), and VA (Vertically Aligned), HAN (Hybrid Aligned Nematic) has been proposed.
A polarizing plate generally comprises a polarizing film and a transparent protective film. The polarizing film is generally obtained by impregnating polyvinyl alcohol with an aqueous solution of iodine or a dichroic dye and further uniaxially stretching the film. The polarizing plate has a configuration in which two transparent protective films are attached to both sides of the polarizing film.

  Optical compensation sheets are used in various liquid crystal display devices in order to eliminate image coloring and expand the viewing angle. As an optical compensation sheet, it has been proposed to use an optical compensation sheet having an optically anisotropic layer formed from liquid crystalline molecules (particularly discotic liquid crystalline molecules) on a transparent support. The optically anisotropic layer is formed by aligning liquid crystalline molecules and fixing the alignment state. In general, the alignment state is fixed by a polymerization reaction using liquid crystalline molecules having a polymerizable group. Liquid crystalline molecules have a large birefringence. The liquid crystal molecules have various alignment forms. By using liquid crystalline molecules, it has become possible to realize optical properties that cannot be obtained with conventional stretched birefringent films.

The optical property of the optical compensation sheet is determined according to the optical property of the liquid crystal cell, specifically, the difference in the display mode. When liquid crystalline molecules, particularly discotic liquid crystalline molecules are used for the optical compensation sheet, optical compensation sheets having various optical properties corresponding to various display modes of the liquid crystal cell can be produced.
Optical compensation sheets using discotic liquid crystalline molecules have already been proposed for various display modes.

  When producing an optical compensation sheet having an optically anisotropic layer in which the orientation of liquid crystalline molecules is fixed on a transparent support, an alignment film is provided between the transparent support and the optically anisotropic layer. In this case, adhesion between the transparent support (usually a cellulose acylate film) and the alignment film is required. In addition, alignment of the alignment film is performed by a process such as rubbing, electric field application, magnetic field application, or light irradiation. However, adhesion of minute dust or the like on the alignment film impairs alignment uniformity. In particular, in the rubbing process, it is necessary to take measures against static electricity generation in order to rub the film surface. For this reason, a water-soluble resin cured film is usually used as the alignment film, and in particular, a cured film made of a hydroxyl group-containing resin such as polyvinyl alcohol and a curing agent is used.

Usually, since a cellulose acylate film used as a transparent support is hydrophobic, it has poor affinity with a water-soluble resin cured film, and in order to eliminate this, an undercoat layer such as gelatin is provided as an adhesive layer (for example, , Patent Document 1), or transparent saponification (especially cellulose acetate film) surface is subjected to alkali saponification treatment to provide adhesion to the support surface to provide an alignment film (for example, see Patent Document 2) A method is disclosed. However, when the gelatin undercoat layer is provided, there is a problem that uniform coating cannot be performed due to the influence of the coating solvent contained in the undercoat layer when the thickness of the support is reduced.
For the alignment film formed of the water-soluble resin cured film coated as described above, rapid curing reaction, humidity resistance dependency after film formation, and the like are important. For example, a method of applying and curing a coating solution in which an acid compound is used in combination with a polyvinyl alcohol resin and a bifunctional aldehyde compound (see Patent Document 3), a coating solution under acidic conditions by adding acid to the modified polyvinyl alcohol and the curing agent A method of applying and curing (see Patent Document 4, paragraph number [0148]) has been proposed.

  A viewing angle is one of the display qualities of a liquid crystal display device. The viewing angle of the liquid crystal display device has a correlation with the tilt angle of the liquid crystal used in the optical compensation sheet, and a wider viewing angle can be obtained by optimizing each liquid crystal display device. Examples of the method for manipulating the tilt angle of the liquid crystal include a method of manipulating the chemical structure such as introduction of a bulky substituent or fluorine group into the molecules used in the alignment film. However, in this method, cost performance increases and adaptability to fine factor fluctuations during manufacturing is low, so a simpler method is desired.

JP 11-248940 A JP 2002-302561 A JP-A-10-2188938 JP 2000-155216 A

However, when these techniques are used, optical defects (for example, surface unevenness, etc.) are likely to occur, and particularly when a long film is manufactured, the yield for obtaining a performance that can be practically used is significantly reduced. There are challenges and it is not enough.
In particular, in recent years, as an optical compensation sheet that can cope with various liquid crystal display devices as described above, a sheet having excellent optical characteristics and a thin film thickness has been strongly desired.
Accordingly, an object of the present invention is to provide an optical compensation sheet that has both good adhesion and good surface condition, and a method for producing the same.
Still another object of the present invention is to provide a liquid crystal display device with high display quality, comprising a polarizing plate in which the optical compensation sheet is disposed on one side of a polarizing film.
Furthermore, another object of the present invention is to provide a liquid crystal display device with high display quality by using an alignment film that enables the operation of the tilt angle of the liquid crystal.

According to the present invention, there are provided an optical compensation sheet having the following configuration, a method for producing the same, a polarizing plate using the optical compensation sheet, and a liquid crystal display device having the polarizing plate disposed therein, thereby achieving the object of the present invention.
(1) An optical compensation sheet in which an alignment film and an optically anisotropic layer obtained by aligning and polymerizing a liquid crystalline compound are laminated in this order on a transparent support that has been previously subjected to adhesion imparting treatment. The film is composed of a layer obtained by heat-curing an alignment film forming composition containing an aldehyde compound having two or more aldehyde groups and one or more nucleophilic agents having a nucleophilic constant (n) of 5 or more and 10 or less. Optical compensation sheet,
(2) The optical compensation sheet according to (1), wherein the nucleophilic agent has a nucleophilic constant (n) of 6.5 or more and 10 or less,
(3) The optical compensation sheet according to (1) or (2) above, wherein the nucleophile is a sulfite that generates sulfite ions or a thiosulfate that generates thiosulfate ions,
(4) The above (1) to (1), wherein the alignment film is a cured film formed by applying and drying an alignment film forming composition containing polyvinyl alcohol and / or modified polyvinyl alcohol as a main component. The optical compensation sheet according to any one of (3),
(5) The optical compensation sheet according to any one of (1) to (4) above, wherein the optically anisotropic layer contains a fluorine-containing surfactant.
(6) The optical compensation sheet according to any one of (1) to (4) above, wherein the optically anisotropic layer contains a fluoroaliphatic group,
(7) Alkali saponification treatment in which the adhesion-imparting treatment applied to the transparent support is a saponification treatment by applying an aqueous solution containing at least a water-soluble organic solvent and a surfactant and / or a compatibilizer. The optical compensation sheet according to any one of (1) to (6) above,
(8) The transparent support described above is characterized in that the Re retardation value is in the range of 0 to 200 nm and the Rth retardation value is in the range of 0 to 400 nm. The optical compensation sheet according to any one of the above,
(9) The above transparent support is a cellulose acylate film, and the cellulose acylate film is a cellulose acylate in a range satisfying the following formulas (1) and (2) at the same time. (1) to the optical compensation sheet according to any one of (8),
Formula (1): 2.3 ≦ SA ′ + SB ′ ≦ 3.0
Formula (2): 0 ≦ SA ′ ≦ 3.0
(In the formula, SA ′ is the substitution degree of the acetyl group substituting the hydrogen atom of the hydroxyl group of cellulose, and SB ′ is the substitution of the acyl group having 3 to 22 carbon atoms substituting the hydrogen atom of the hydroxyl group of cellulose. Represents degree.)
(10) The optical system according to any one of (1) to (9), wherein the tilt angle of the liquid crystalline compound on the alignment film side is manipulated by adding the nucleophile to the alignment film. Compensation sheet.
(11) An orientation containing at least one aldehyde compound having two or more aldehyde groups and one or more nucleophiles having a nucleophilic constant (n) of 5 or more and 10 or less on a transparent support that has been previously subjected to adhesion imparting treatment. Applying a film-forming composition, heating and hardening to form an alignment film, applying a composition containing a liquid crystalline compound, aligning the liquid crystalline compound, and polymerizing the optically different compound. A method for producing an optical compensation sheet having the steps of forming an isotropic layer in this order;
(12) In the method for producing an optical compensation sheet having an alignment film and an optically anisotropic layer on a transparent support, the alignment film is formed by applying the alignment film-forming composition by a die coater method. The method for producing an optical compensation sheet according to any one of (1) to (10),
(13) In the die coater coating method described in (12) above, the land of the tip lip of the slot die is brought close to the surface of the transparent support that is supported by the backup roll and continuously runs, and is applied from the slot of the tip lip. In the method of applying the liquid, a slot die having a land length in the web traveling direction of the tip lip on the transparent die traveling direction side of the slot die was used, and the slot die was set at the application position. Sometimes, a coating apparatus is used in which the gap between the tip lip on the opposite side to the web traveling direction and the web is 30 μm or more and 120 μm or less larger than the gap between the tip lip on the web traveling direction side and the web. The method for producing an optical compensation sheet according to (12), wherein
(14) A polarizing plate, wherein a transparent protective film, a polarizing film, and the optical compensation sheet according to any one of (1) to (10) are laminated in this order,
(15) The polarizing plate according to (14), wherein the transparent protective film of the polarizing plate according to (14) is provided with an antireflection film on the air side surface of the protective film,
(16) In a liquid crystal display device comprising a polarizing film and a polarizing plate comprising two transparent protective films disposed on both sides thereof, disposed on both sides of the liquid crystal cell, the polarizing film is disposed between the liquid crystal cell and the polarizing plate. At least one of the two transparent protective films is the optical compensation sheet according to any one of (1) to (10),
(17) The liquid crystal display device according to (16), which is a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, ECB, and OCB modes .

The optical compensation sheet of the present invention has a layer structure in which a transparent support, an alignment film, and an optically anisotropic layer that have been subjected to adhesion treatment in advance are laminated in this order, and the alignment film has two or more aldehyde groups. The alignment film thus obtained has excellent adhesion to the transparent support and has optical properties such as planar unevenness by containing an aldehyde compound having a nucleophilic compound and one nucleophilic agent having a nucleophilic constant (n) of 5 or more. An optical compensation sheet that reduces or eliminates mechanical defects can be stably obtained. That is, the optical compensation sheet of the present invention is an optical compensation sheet that achieves both adhesion and good surface condition. The alignment film forming composition is applied using a composition containing at least one aldehyde compound having two or more aldehyde groups and a nucleophile having a nucleophilic constant (n) of 5 or more. By heating and curing, the alignment film is cured uniformly throughout, and even with rubbing, a uniform alignment state is formed on the entire film surface, and the coating liquid for the optically anisotropic layer is uniformly distributed over the entire coated surface. It is presumed that the progress of application is one of the main factors.
In addition, according to the present invention, there is provided a polarizing plate in which the optical compensation sheet is disposed on one side of the polarizing film, and a high-quality liquid crystal display device including the polarizing plate is provided.

Hereinafter, the optical compensation sheet of the present invention, a method for producing the same, a polarizing plate using the optical compensation sheet, and a liquid crystal display device having the polarizing plate will be described in detail.
First, an optical compensation sheet and a manufacturing method thereof will be described. As described above, in the optical compensation sheet of the present invention, the transparent support, the alignment film, and the optically anisotropic layer (also referred to as “optically anisotropic layer”) that have been subjected to adhesion treatment in advance are laminated in this order. Layer structure.

[Transparent support]
The transparent support of the present invention is preferably glass or a transparent polymer film. The transparent support preferably has a light transmittance of 80% or more. Examples of the polymer constituting the polymer film include cellulose esters (eg, cellulose mono- or triacylate), and norbornene-based polymers such as ARTON and ZEONEX (both are trade names). Moreover, even if it is a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence, it is possible to develop birefringence by modifying the molecule as described in International Publication No. 00/26705 pamphlet. Can be used for the optical film of the present invention.
As the polymer film of the present invention, a cellulose ester film is preferable, and a cellulose acetate film is more preferable.
The thickness of the transparent support of the present invention is preferably 20 to 500 μm, more preferably 40 to 200 μm, and most preferably 30 to 80 μm.

In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth (λ) is light having a wavelength of λ nm from the direction inclined by + 40 ° with respect to the normal direction of the film, with Re (λ) and the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). And a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation values measured in three directions in total. Here, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. Those whose average refractive index is not known 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 calculates nx, ny, and nz by inputting these assumed values of average refractive index and film thickness.
The retardation value of the polymer film varies in a preferred range depending on the liquid crystal display device in which the optical compensation sheet is used and the method of use thereof. Usually, the Re retardation value is 0 to 200 nm, and the Rth retardation value is 0 to 0. It is preferable to adjust to the 400 nm range.

When two optically anisotropic layers are used in the liquid crystal display device, the Rth retardation value of the polymer film is preferably in the range of 30 to 250 nm. When one optically anisotropic layer is used in the liquid crystal display device, the Rth retardation value of the polymer film is preferably in the range of 0 to 400 nm.
The birefringence (Δn: nx−ny) of the polymer film is preferably in the range of 0 to 0.020. The birefringence {(nx + ny) / 2−nz} in the thickness direction of the polymer film is preferably in the range of 0 to 0.04.
In order to adjust the retardation value of a polymer film, a method of applying an external force such as stretching is generally used. As another method, a retardation increasing agent for adjusting optical anisotropy is optionally added. The

The cellulose acylate used in the present invention includes, as raw materials, 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 the present invention, cellulose acylate is produced by esterification from cellulose. However, the above-mentioned particularly preferable cellulose is not always usable as it is, and linter, kenaf and pulp are purified and used.

In the present invention, cellulose acylate refers to a carboxylic acid ester of cellulose. The total carbon number of the carboxylic acid is preferably 2-22.
The cellulose acylate of the present invention preferably has a degree of substitution with a hydroxyl group of cellulose satisfying the following mathematical formulas (1) and (2).
Formula (1): 2.3 ≦ SA ′ + SB ′ ≦ 3.0
Formula (2): 0 ≦ SA ′ ≦ 3.0

Here, SA ′ is the substitution degree of the acetyl group substituting the hydrogen atom of the hydroxyl group of cellulose, and SB ′ is the substitution degree of the acyl group having 3 to 22 carbon atoms substituting the hydrogen atom of the hydroxyl group of cellulose. Represents. SA represents an acetyl group substituting a hydrogen atom of a hydroxyl group of cellulose, and SB represents an acyl group having 3 to 22 carbon atoms substituting a hydrogen atom of a hydroxyl group of cellulose.
Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by esterifying some or all of these hydroxyl groups with acyl groups. The degree of acyl substitution means the proportion of cellulose esterified at each of the 2-position, 3-position and 6-position (100% esterification at each position is substitution degree 1).

In the present invention, the total sum of substitution degrees of SA and SB (SA ′ + SB ′) is more preferably 2.6 to 3.0, and particularly preferably 2.80 to 3.00.
Further, the substitution degree (SB ′) of SB is more preferably 0 to 1.2, particularly 0 to 0.8.
The acyl group (SB) having 3 to 22 carbon atoms of the cellulose acylate used in the present invention may be an aliphatic group or an aryl group, and is not particularly limited. They are, for example, alkyl carbonyl esters, alkenyl carbonyl esters, cycloalkane carbonyl esters, aromatic carbonyl esters, aromatic alkyl carbonyl esters and the like of cellulose, and each may further have a substituted group. These preferred SBs include propionyl, butanoyl, keptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, cyclohexanecarbonyl, oleoyl, (meth) acryloyl, phenylacetyl, benzoyl. , Naphthylcarbonyl, cinnamoyl group and the like. Among these, preferable SB is propionyl, butanoyl, pentanoyl, hexanoyl, cyclohexanecarbonyl, dodecanoyl, octadecanoyl, oleoyl, (meth) acryloyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like.
More preferred are lower fatty acid esters of cellulose.
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). Cellulose acetate is preferred as the cellulose ester, 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.
Specific methods for synthesizing these acyl groups and cellulose acylate are disclosed in JIII Journal of Technical Disclosure No. 2001-1745 (Invention Association, March 15, 2001) p. 9 is described in detail.

In cellulose acetate, the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are not evenly substituted, but the substitution degree at the 6-position tends to be small. In the cellulose acetate used in the present invention, it is preferable that the degree of substitution at the 6-position of cellulose is the same or greater than that at the 2- and 3-positions.
The ratio of the substitution degree at the 6-position to the total substitution degree at the 2-position, the 3-position, and the 6-position is preferably 30 to 40%, more preferably 31 to 40%, and more preferably 32 to 40%. Most preferably it is. The substitution degree at the 6-position is preferably 0.88 or more.

  The cellulose acylate film is preferably composed of cellulose acylate in which the polymer component constituting the film substantially has the above definition. “Substantially” means 55% by weight or more (preferably 70% by weight or more, more preferably 80% by weight or more) of the total polymer components (polymer components other than particles described later).

The polymerization degree of the cellulose acylate is a viscosity average polymerization degree of 200 to 700, preferably 230 to 550, more preferably 230 to 350, and particularly preferably a viscosity average polymerization degree of 240 to 320. The average degree of polymerization can be measured by Uda et al.'S intrinsic viscosity method (Kazuo Uda, Hideo Saito, Journal of Textile Society, Vol. Further details are described in JP-A-9-95538.
The molecular weight distribution of cellulose acylate preferably used in the present invention is evaluated by gel permeation chromatography, and its polydispersity index Mw / Mn (Mw is weight average molecular weight, Mn is number average molecular weight) is small, and molecular weight distribution. Is preferably narrow. 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 2.0. preferable.
As for the cellulose acylate, the raw material cotton and the synthesis method thereof are those described in the above public technical number 2001-1745 p. 7-12.

As described above, the retardation increasing agent can be used to increase the retardation in the thickness direction of the transparent support. As the retardation increasing agent, a compound having at least two aromatic rings and a molecular structure that does not sterically hinder the conformation of the two aromatic rings can be used. The aromatic compound is used in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of cellulose acylate. The aromatic compound is preferably used in an amount of 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of cellulose acylate. Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring.
Examples of the retardation increasing agent include compounds described in European Patent 0911656A2, JP-A Nos. 2000-1111914, 2000-275434, and the like.

It is preferable to add fine particles to the cellulose acylate film of the present invention in order to maintain good scratch resistance and film transportability.
They are conventionally used as matting agents, anti-blocking agents or anti-scratching agents. Although they are not particularly limited as long as they are materials exhibiting the above-mentioned functions, preferred specific examples of these matting agents include compounds containing silicon, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, oxidation as inorganic compounds. Barium, zirconium oxide, 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. More preferred is an inorganic compound containing silicon or zirconium oxide, but silicon dioxide is particularly preferred because the turbidity of the cellulose acylate film can be reduced.
Surface-treated inorganic fine particles are also preferable because of good dispersibility in cellulose acylate. Examples of the treatment method include the method described in JP-A No. 54-57562. Examples of the particles include those described in JP-A No. 2001-151936.
As the organic compound, for example, polymers such as cross-linked polystyrene, silicone resin, fluororesin and acrylic resin are preferable, and among them, silicone resin is preferably used. Among silicone resins, those having a three-dimensional network structure are particularly preferable.

  A plasticizer can be added to the cellulose acylate film of the present invention in order to improve mechanical properties or to improve the drying speed. As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Specifically, the content described in detail on page 16 of the Japan Society for Invention and Innovation Technical Report (Technology Number 2001-1745, Invention Association issued on March 15, 2001) is preferably used. The addition amount of the plasticizer is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 3 to 15% by weight of the amount of the cellulose ester.

The cellulose acylate film of the present invention is further added with a deterioration inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) and UV inhibitor. May be. Examples of the deterioration inhibitor include compounds described in JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by weight of the solution (dope) to be prepared, and more preferably 0.01 to 0.2% by weight. As a particularly preferred example of the deterioration preventing agent, butylated hydroxytoluene (BHT) can be mentioned. Examples of the ultraviolet light inhibitor include compounds described in JP-A-7-11055 and JP-A-7-11056.
Further, for these details, materials described in detail on pages 17 to 22 of the above-mentioned public technical number 2001-1745 are preferably used.

  In order to reduce the dimensional change due to moisture absorption of the produced cellulose acylate film, 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. The amount of these compounds added is preferably in the range of 0.01 to 10% by weight with respect to the solution (dope) to be adjusted. Further, the free volume in the cellulose acylate film may be reduced. Specifically, the smaller the amount of residual solvent during film formation by the solvent casting method described later, the smaller the free volume. It is preferable to dry under the condition that the residual solvent amount with respect to the cellulose acylate film is in the range of 0.01 to 1.00% by weight.

[Method for producing transparent support]
In the present invention, it is preferable to produce a cellulose acylate film by a solvent cast method, and the film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.
Examples of the organic solvent to be used include conventionally known organic solvents. For example, those having a solubility parameter in the range of 17 to 22 are preferable. The solubility parameter represents, for example, those described in “Polymer Handbook (4th. Edition)”, VII / 671 to VII / 714 by J. Brandrup, E. H and the like. Lower aliphatic hydrocarbon chloride, lower aliphatic alcohol, ketone having 3 to 12 carbon atoms, ester having 3 to 12 carbon atoms, ether having 3 to 12 carbon atoms, aliphatic having 5 to 8 carbon atoms Examples thereof include hydrocarbons and aromatic hydrocarbons having 6 to 12 carbon atoms.
The 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, detailed compounds can be mentioned on pages 12 to 16 of the aforementioned technical number 2001-1745.

In particular, in the present invention, the solvent is preferably used by mixing two or more kinds of organic solvents, and particularly preferred organic solvents are three or more kinds of mixed solvents different from each other, and the first solvent has the number of carbon atoms. 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 acetoacetic acid ester; It is preferably selected from alcohol having a boiling point of 30 to 170 ° C or hydrocarbon having a boiling point of 30 to 170 ° C.
In particular, it is preferable from the viewpoint of the solubility of cellulose acetate to use 20 to 90% by weight of acetate, 5 to 60% by weight of ketones, and 5 to 30% by weight of alcohols.

  In addition to the organic solvent of the present invention, the dope used in the present invention may contain fluoroalcohols in an amount of 10% by weight or less, more preferably 5% by weight or less of the total organic solvent amount of the present invention. It is preferable for improving the solubility and speeding up the solubility. Fluoroalcohols having a boiling point of 165 ° C. or lower are preferred, preferably 111 ° C. or lower, and more preferably 80 ° C. or lower. The fluoroalcohols preferably have about 2 to 10 carbon atoms, more preferably about 2 to 8 carbon atoms. The fluoroalcohols are fluorine atom-containing aliphatic alcohols that may or may not have a substituent. As the substituent, an aliphatic substituent or an aromatic substituent containing or not containing a fluorine atom is preferable.

  Examples of the fluoroalcohols include compounds described in paragraph No. [0020] in JP-A-8-143709, paragraph No. [0037] in JP-A-11-60807, and the like. These fluoroalcohols may be used alone or in combination.

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. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by weight (preferably less than 2% by weight). Moreover, it is preferable that halogenated hydrocarbons such as methylene chloride are not detected at all from the produced cellulose acetate film.

  Specific examples of the organic solvent used in the present invention include paragraph numbers [0021] to [0025] of JP-A No. 2002-146043 and paragraph numbers [0016] to [0021] of JP-A No. 2002-146045. ] And the like.

  When preparing the cellulose acylate solution of the present invention, the container may be filled with an inert gas such as nitrogen gas. The viscosity of the cellulose triacetate solution immediately before film formation may be in a range that allows casting, and is usually adjusted to a range of 10 to 2000 Pa · s, particularly preferably 30 to 400 Pa · s. .

  Regarding the preparation of the cellulose acylate solution (dope) according to the present invention, the dissolution method is not particularly limited, and may be a room temperature dissolution method, a cooling dissolution method or a high temperature dissolution method, or a combination thereof. With respect to these, 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, Special Examples include methods for preparing cellulose acylate solutions described in JP 2000-273184 A, JP 11-323017 A, JP 11-302388 A, and the like. The above-described method for dissolving cellulose acylate in an organic solvent can appropriately apply these techniques also in the present invention. Further, the dope solution of cellulose acylate is usually concentrated and filtered, and similarly described in detail on page 25 of the aforementioned technical number 2001-1745. 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 film using a cellulose acylate solution will be described. As a method and equipment for producing a cellulose acylate film, 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 cellulose triacetate film are used. The film forming process will be described by taking the band method as an example. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in the storage kettle, and the bubbles contained in the dope are defoamed to finish. Prepare. The prepared dope is fed from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the rotational speed, and the dope is run endlessly from the die (slit) of the pressure die. The dope film (also referred to as a web) is peeled off from the metal support at the peeling point where the metal support is almost cast around the metal support. Both ends of the obtained web are sandwiched between clips, transported by a tenter while keeping the width, dried, then transported by a roll group of a drying device, dried, and wound up to a predetermined length by a winder. The combination of the tenter and the roll group dryer varies depending on the purpose. Each of these manufacturing processes (casting (including co-casting), metal support, drying, peeling, stretching, etc.) is described in detail on pages 25 to 30 of the aforementioned technical number 2001-1745. The contents made are mentioned. In the casting step, one type of cellulose acylate solution may be cast in a single layer, or two or more types of cellulose acylate solutions may be cast simultaneously and / or sequentially.

  Furthermore, the cellulose acylate solution of the present invention can 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).

  In the conventional single-layer liquid, it is necessary to extrude a cellulose acylate solution having a high concentration and a high viscosity in order to obtain a required film thickness. In many cases, a problem occurred due to the occurrence of an object, a fault, or poor flatness. As a solution to this, by casting a plurality of cellulose acylate solutions from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time, producing a flat film with improved flatness. Not only can this be achieved, but the use of a concentrated cellulose acylate solution can achieve a reduction in drying load and increase the production speed of the film.

[Characteristics of cellulose acylate film]
The film of the present invention preferably has the following physical characteristics together with the hygroscopic expansion coefficient.
(Film surface properties)
The surface of the cellulose acylate film of the present invention has an arithmetic average roughness (Ra) of surface irregularities of the film based on JIS B0601-1994 of 0.1 μm or less and a maximum height (Ry) of 0.5 μm or less. It is preferable. More preferably, the arithmetic average roughness (Ra) is 0.05 μm or less, and the maximum height (Ry) is 0.2 μm or less.
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 film of the present invention containing fine particles, which are the main composition that keeps the mechanical properties of the film having a film thickness of less than 80 μm within the following range, within the size of the irregularities described later, In providing adhesion to the film surface and applying an alignment film, the entire surface of the film is processed stably and uniformly, and optical defects due to processing unevenness, coating unevenness and the like are eliminated, which is preferable.

  Moreover, it is preferable that the dynamic friction coefficient of the transparent support body used for this invention is 0.4 or less, and it is especially preferable that it is 0.3 or less. If the coefficient of dynamic friction is within the above range, the friction with the transport roll is small, dust generation from the support does not occur, there is little adhesion of foreign matter on the film, and there are point defects and coating streaks on the optical compensation sheet. This is preferable because the frequency does not exceed the allowable value. The dynamic friction coefficient can be measured by a steel ball method using a 5 mmφ steel ball.

(Haze of film)
The haze of the cellulose acylate film of the present invention is preferably 0.01 to 2.0%. More preferably, it is 0.05-1.5%, More preferably, it is 0.1-1.0%. In this range, the transparency of a film important as an optical film can be sufficiently secured, which is preferable. The haze can be measured by measuring the cellulose acylate film sample 40 mm × 80 mm of the present invention at 25 ° C. and 60% RH with a haze meter (HGM-2DP, Suga Test Instruments) according to JIS K-6714.

(curl)
The curl value in the width direction of the transparent support used in the present invention is preferably -7 / m to + 7 / m. When the transparent support of the present invention is subjected to surface treatment, rubbing treatment and alignment film, optical anisotropic layer, etc., which will be described later, on a long and wide transparent support, the width direction of the transparent support If the curl value is outside the above range, film handling may be hindered and the film may be cut. In addition, the film is strongly in contact with the transport roll at the edge and center of the film, so it is easy to generate dust, and foreign matter adheres to the film more frequently. It became clear that the value was exceeded.
When the cellulose acylate film of the present invention is subjected to surface treatment, rubbing treatment and alignment film, optically anisotropic layer, etc., which will be described later, on a long and wide transparent film, the width direction of the transparent film When the curl value is within the above-mentioned range, the film is handled easily and the film is not cut. Also, at the edge and center of the film, the film will come into strong contact with the transport rolls to prevent dust generation and foreign matter adhesion to the film will not occur, and the frequency of point defects and coating streaks on the optical compensation sheet will be allowed. Can be within range. Further, by setting the curl in the above-mentioned range, it is possible to reduce color spot failures that are likely to occur when the optically anisotropic layer is installed, and it is possible to prevent bubbles from entering when the polarizing film is bonded, which is preferable.
The curl value can be measured according to a measurement method (ANSI / ASCPH1.29-1985) defined by the American National Standards Institute.

(Hygroscopic expansion coefficient of film)
The cellulose acylate film of the present invention preferably has a hygroscopic expansion coefficient of 30 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is more preferably 15 × 10 ⁻⁵ /% RH or less, and further preferably 10 × 10 ⁻⁵ /% RH or less. The hygroscopic expansion coefficient is preferably small, but usually it is 1.0 × 10 ⁻⁵ /% RH or more. 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 this 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 sheet.
The method for measuring the hygroscopic expansion coefficient is shown below. A sample having a width of 5 mm and a length of 20 mm was cut out from the produced cellulose acylate film, and one end was fixed and hung in an atmosphere of 25 ° C. and 20% RH (R0). A weight of 0.5 g was hung from the other end and left for 10 minutes to measure the length (L0). Next, the length (L1) was measured while maintaining the temperature at 25 ° C. and the humidity at 80% RH (R1). 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] = {(L1-L0) / L0} / (R1-R0)

(Water permeability of film)
The moisture permeability of the cellulose acylate film of the present invention is measured under conditions of a temperature of 60 ° C. and a humidity of 95% RH based on JIS standard JIS Z0208, and converted to a film thickness of 80 μm, 400 to 2000 g / m ² · 24 h. It is preferable that More preferably 500~1800g / m ² · 24h, and particularly preferably 600~1600g / m ² · 24h.
When the moisture permeability is in the above range, the absolute value of the humidity dependence of the Re value and Rth value of the film is as low as 0.5 nm /% RH or less, and an optically anisotropic layer is laminated on the cellulose acylate film. Even when an optical compensation sheet is used, the absolute value of the humidity dependence of the Re value and Rth value is as low as 0.5 nm /% RH or less. Therefore, the optical compensation sheet and a polarizing plate using the optical compensation sheet are incorporated in a liquid crystal display device. In this case, it is preferable because it does not cause a change in color and a decrease in viewing angle. In addition, when a polarizing plate is produced by attaching an optical compensation sheet to both surfaces of a polarizing film, there is no fear that the cellulose acylate film hinders the drying of the adhesive and causes poor adhesion.

If the film thickness of the cellulose acylate film is thick, the moisture permeability becomes small, and if the film thickness is thin, the moisture permeability becomes large. Therefore, it is necessary to convert the sample of any film thickness to a standard of 80 μm. Conversion of the film thickness is obtained as (water vapor permeability in terms of 80 μm = measured moisture permeability × measured film thickness μm / 80 μm).
The measurement method of moisture permeability is “Polymer Physical Properties II” (Polymer Experiment Course 4, Kyoritsu Shuppan), pages 285-294: Measurement of vapor permeation amount (mass method, thermometer method, vapor pressure method, adsorption amount method) The cellulose acylate film sample 70 mmφ of the present invention was conditioned at 25 ° C., 90% RH, 60 ° C., and 95% RH for 24 hours, respectively, and a moisture permeation test apparatus (KK-709007) was applied. , Toyo Seiki Co., Ltd.) calculates the amount of water per unit area (g / m ² ) according to JIS Z-0208, and obtains moisture permeability = weight after humidity adjustment−weight before humidity adjustment.

(Retention of film)
The weight change of the film when the cellulose acylate film of the present invention is allowed to stand for 48 hours under the conditions of “80 ± 5 ° C., 90 ± 10% RH” is preferably 0 to 2%.
<Method for evaluating retention>
The sample was cut into a size of 10 cm × 10 cm, and the weight after being allowed to stand for 24 hours in an atmosphere of 23 ° C. and 55% RH was measured, and left for 48 hours under the conditions of 80 ± 5 ° C. and 90 ± 10% RH. . The surface of the sample after the treatment is lightly wiped, the weight after standing for 1 day at 23 ° C. and 55% RH is measured, and the retention property is calculated by the following method.
Retention property (% by weight) = {(weight before being left−weight after being left) / weight before being left} × 100

(Dimensional change of film)
The dimensional stability of the cellulose acylate film of the present invention is as follows: dimensional change rate after standing for 24 hours under the conditions of 60 ° C. and 90% RH (high humidity) and the condition of 90 ° C. and 5% RH. It is preferable that the dimensional change rate after standing for 24 hours (high temperature) is 0.5% or less. More preferably, it is 0.3% or less, More preferably, it is 0.15% or less.

<Measurement method of dimensional change rate>
Prepare two cellulose acylate film samples 30mm x 120mm, adjust the humidity at 25 ° C and 60% RH for 24 hours, and use automatic pin gauge (Shinto Kagaku Co., Ltd.) with 6mmφ holes at both ends at 100mm intervals. It was opened and the original size (L0) of the punch interval was used. Punch interval size (L1) after one sample was treated at 60 ° C. and 90% RH for 24 hours, punch after one sample was treated at 90 ° C. and 5% RH for 24 hours The spacing dimension (L2) was measured. Measurement was made to a minimum scale of 1/1000 mm at all intervals. Dimensional change rate of 60 ° C. and 90% RH (high humidity) = {| L0−L1 | / L0} × 100, Dimensional change rate of 90 ° C. and 5% RH (high temperature) = {| L0−L2 | / The dimensional change rate was determined as L0} × 100.

(Tear strength)
As described above, the transparent support has a thickness of 20 to 80 μm, and has a tear strength of 2 g or more based on the tear test method (Elmendorf tear method) of JIS K7128-2: 1998. Is preferable in that the strength of the film can be sufficiently maintained. More preferably, it is 5-25g, More preferably, it is 6-25g. Moreover, in 60 micrometer conversion, 8 g or more is preferable, More preferably, it is 8-15 g.
Specifically, it can be measured using a light load tear strength tester after conditioning a sample piece of 50 mm × 64 mm under the conditions of 25 ° C. and 65% RH for 2 hours.
In particular, the curl and tear strength are within the above ranges when the transparent support obtained by finishing a predetermined manufacturing process is a long product having a length of 100 to 5000 m and a width of 0.7 or more. It is preferable to do this.

(Scratch strength)
The scratch strength is preferably 1 g or more, more preferably 5 g or more, and particularly preferably 10 g or more. By setting it in this range, scratch resistance and handling properties of the film surface can be maintained without problems, which is preferable.
The scratch strength can be evaluated with a load (g) that allows the surface of the support to be scratched using a sapphire needle having a cone apex angle of 90 degrees and a tip radius of 0.25 m, and the scratch mark can be visually confirmed.

[Method of imparting adhesion of transparent support]
In the case where the alignment film is provided by a coating method, the transparent support of the present invention imparts adhesion to the surface of the transparent support and is subjected to a surface treatment so that the alignment film coating solution is uniformly applied. Is preferred.
Examples of the surface treatment method include a method of providing an undercoat layer of the alignment film. A single-layer method in which only one layer of 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 the first layer is well adhered to a polymer film A layer (hereinafter abbreviated as the undercoat first layer) is applied, and a hydrophilic resin layer such as gelatin (hereinafter abbreviated as the undercoat second layer) is applied thereon as the second layer. The contents of the multilayer method (for example, described in JP-A No. 11-248940) can be mentioned.
Examples of other surface treatment include a method of modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali treatment, and the like. Details of these are described in detail on pages 30 to 32 of the above-mentioned official technical number 2001-1745. Among these, alkali saponification treatment is particularly preferable, and it is extremely effective as the surface treatment of the cellulose acetate film.

[Alkaline saponification]
The alkali saponification treatment is performed by immersing, spraying or coating an alkali solution on a transparent support. Preferably, a saponification treatment is performed by application described later.

[Alkaline solution]
The alkaline solution is preferably an alkaline solution having a pH of 11 or higher. More preferably, the pH is 12-14.
Examples of the alkaline agent used in the alkaline solution include inorganic alkaline agents such as sodium hydroxide, potassium and lithium, 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 Organic alkali agents such as hydroxide are also used. These alkali agents can be used alone or in combination of two or more, and a part of them may be added in the form of a salt, for example, 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 used, the reaction temperature, and the reaction time. 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 solvent of the alkaline solution of the present invention is preferably composed of a mixed solution of water and a water-soluble organic solvent. As the organic solvent, any organic solvent miscible with water can be used, but those having a boiling point of 120 ° C. or lower, more preferably 100 ° C. or lower are 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 ] ^1/2 . More preferably, the I / O value is 0.6 to 10, and the solubility parameter is 18 to 31 [mJ / m ³ ] ^1/2 . When the I / O value and the solubility parameter are in this range, the alkali saponification rate is appropriate, the uniformity of the entire surface of the saponification is sufficient, and haze does not occur.
In addition, when an organic solvent, particularly an organic solvent in each of the above-mentioned organic and soluble ranges, is used in combination with a surfactant, a compatibilizing agent, etc. described later, a high saponification rate is maintained and the saponification degree over the entire surface is maintained. It is preferable because the uniformity is improved.

  Examples of the organic solvent having preferable characteristic values include those described in “Synthetic Organic Chemistry Association”, “New Edition Solvent Pocket Book” (Ohm Co., Ltd., published in 1994) and the like. The inorganic / organic value (I / O value) of the organic solvent is described, for example, in Yoshio Tanaka “Organic Conceptual Diagram” (Sankyo Publishing Co., Ltd., 1983, pages 1-31).

  Specifically, monohydric aliphatic alcohols (eg, methanol, ethanol, propanol, butanol, pentanol, hexanol, etc.), alicyclic alkanols (eg, cyclohexanol, methylcyclohexanol, methoxycyclohexanol, cyclohexylmethanol, Cyclohexylethanol, cyclohexylpropanol, etc.), phenylalkanols (eg, benzyl alcohol, phenylethanol, phenylpropanol, phenoxyethanol, methoxybenzyl alcohol, benzyloxyethanol, etc.), heterocyclic alkanols (furfuryl alcohol, tetrahydrofurfuryl alcohol) Etc.), monoethers of glycol compounds (methyl cellosolve, ethyl cellosolve, propyl cellosolve, methoxymethoxyethane) Butyl cell sorb, hexyl cell sorb, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, methoxy triglycol, ethoxy triglycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Ethers, etc.) ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), amides (eg, N, N-dimethylformamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, etc. ), Sulfoxides (eg, dimethyl sulfoxide) and ethers (eg, tetrahydrofuran, pyran, dioxane, trioxane, dimethyl cellosolve, diethyl cellosolve, dip Piruserusorubu, 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 the organic solvent is used singly or when two or more organic solvents are mixed, those having high solubility in water are preferable. The solubility of the organic solvent in water is preferably 50% by weight or more, and more preferably freely mixed with water. Thereby, an alkali solution having sufficient solubility in an alkali agent, a salt of a fatty acid by-produced by a saponification treatment, a salt of carbonic acid generated by absorbing carbon dioxide in the air, and the like can be prepared.
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 of water and organic solvent is preferably 3/97 to 85/15 weight ratio. More preferably, it is 5 / 95-60 / 40 weight ratio, More preferably, it is 15 / 85-40 / 60 weight ratio. In this range, the entire surface of the film is easily saponified uniformly without impairing the optical properties of the cellulose acylate film, which is preferable.

  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 used as a dissolution aid for the surfactant and compatibilizer described later. You may use together as an agent. The content is preferably 0.1 to 5% with respect to the total weight 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. There is no restriction | limiting in particular in surfactant to be used, Any of anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, a fluorine-type surfactant, etc. may be sufficient.

Specifically, for example, Tokiyuki Yoshida “Surfactant Handbook (new edition)” (Engineering Book, 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.
In the alkaline solution, it is also preferable to use a nonionic surfactant and an anionic surfactant or a nonionic masking surfactant and a cationic surfactant in coexistence because the effect of the present invention is enhanced.

  The amount of these surfactants to be added to the alkaline solution is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

  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. For example, a water-soluble polymer containing a repeating unit having a hydroxyl group and / or an amide group, such as a polyol compound or a saccharide, can be preferably mentioned. .
As the polyol compound, any of a low molecular compound, an oligomer compound, and a high molecular compound can be used.
Examples of aliphatic polyols include alkanediols having 2 to 8 carbon atoms (for example, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerin monomethyl ether, glycerin monoethyl ether, cyclohexanediol, cyclohexanedimethanol). , Diethylene glycol, dipropylene glycol, etc.), C3-C18 alkanes containing 3 or more hydroxyl groups (for example, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, diglycerin) , Dipentaerythritol, inositol, etc.).
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 these, saccharides having no free aldehyde group and ketone group and not showing reducibility are preferable.
Saccharides are generally classified into glucose, sucrose, trehalose type oligosaccharides in which reducing groups are bonded to each other, glycosides in which a reducing group of saccharides and non-saccharides are combined, and sugar alcohols reduced by hydrogenation of saccharides. Both are suitably used in the present invention.
For example, saccharose, trehalose, alkyl glycoside, phenol glycoside, mustard oil glycoside, D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit , D, L-Tallit, Zulsicit, 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 repeating unit having a hydroxyl group and / or an amide group include natural gums (for example, gum arabic, guar gum, tragand gum, etc.), polyvinyl pyrrolidone, dihydroxypropyl acrylate polymers, celluloses. Alternatively, addition reactants of chitosans and epoxy compounds (ethylene oxide or propylene oxide) can be mentioned.
Of these, polyol compounds such as alkylene polyols, polyalkyleneoxy polyols and sugar alcohols are preferred.

  The content of the compatibilizer is preferably 0.5 to 25% by weight and more preferably 1 to 20% by weight with respect to the alkaline solution.

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

[Alkali saponification method]
The surface treatment method of the cellulose acylate film using the above alkaline solution may be any conventionally known method, but in particular, when only one surface of the film is uniformly saponified without unevenness, the coating method is preferable. As a coating method, a conventionally known coating method {rod coating method (rod wound with a thin metal wire), roll coating method (forward roll coater, reverse roll coater, gravure coater), curtain coating method, die coating method ( Coating methods such as extrusion coater (slot coater), slide coater, slit die coater). The coating method is described in various documents (for example, Modern Coating and Drying Technology, Edward Cohen and Edgar B. Gutoff, Edits., VCH Publishers, Inc, 1992). The coating amount of the alkali solution, then, taking into account the waste treatment to water washing removed as much as possible it is desirable to suppress, preferably ^{1~100cc / m 2, 1~50cc / m} 2 is more preferable. A rod coater, gravure coater, blade coater and die coater that can be stably operated even in a small coating amount range are preferred. In particular, a die coater in which the coating device portion and the coating support surface can be applied at high speed without causing uneven coating stripes in a small coating amount region is preferable.
The saponification treatment is preferably performed at a treatment temperature that does not exceed 120 ° C., which is a temperature at which deformation of the film to be treated, alteration of the treatment liquid, and the like do not occur. Further, the temperature is preferably 10 ° C. or higher and 100 ° C. or lower. In particular, a temperature of 20 to 80 ° C. is preferable.
The saponification time is determined by appropriately adjusting the alkali solution and the processing temperature, but it is preferably performed in the range of 1 second to 60 seconds.

Further, the step of saponifying the cellulose acylate film with an alkali solution at a surface temperature of at least 10 ° C., the step of maintaining the temperature of the cellulose acylate film at least at 10 ° C., and the alkali solution to the cellulose acylate film It is preferable to carry out an alkali saponification treatment by a step of rinsing off.
The step of saponifying the cellulose acylate film with an alkaline solution at a predetermined temperature on the surface thereof includes 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 The process etc. which combined these are mentioned. It is preferable to combine with a step of adjusting to a predetermined temperature before coating.
After the saponification reaction, it is preferable to wash and remove the alkaline solution and the saponification reaction product from the film surface by washing with water, neutralizing and washing with water.
Specifically, for example, the contents described in International Publication No. 02/46809 pamphlet, Japanese Patent Application Laid-Open No. 2003-313326, and the like can be given.
The surface of the film on which the hydrophilic treatment has been performed preferably has a contact angle with water on the film surface in the range of 20 to 55 °. The contact angle with water is more preferably in the range of 25 to 50 °, and particularly preferably in the range of 30 to 45 °. The surface energy on the film surface is preferably in the range of 55 to 75 mN / m. The evaluation method of the surface energy [Evaluation Item 2] of the surface characteristics can be obtained by the contact angle method, the wet heat method, and the adsorption method described in “Basics and Applications of Wetting” (Realize, 1989).
By satisfying such surface characteristics, the adhesion to the alignment film and the polarizing film is sufficient, and when the polarizing plate of the present invention is used for an image display device, optical such as a bright spot failure and a cloud failure It exhibits excellent characteristics with no typical defects.

[Alignment film]
The alignment film of the present invention is preferably an alignment film formed by applying an organic compound (preferably polymer) coating solution. From the viewpoints of the strength of the alignment film itself and the adhesion to the optically anisotropic layer as the lower layer or the upper layer, a cured polymer film is preferable. The alignment film is provided in order to define the alignment direction of the liquid crystal compound provided thereon. Examples of methods for imparting an orientation-defining function to the alignment film include conventionally known rubbing, magnetic field or electric field application, 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 (eg, VA, OCB, HAN) in which many rod-like liquid crystal molecules in the liquid crystal cell are aligned substantially vertically, the liquid crystal molecules in the optically anisotropic layer are aligned substantially horizontally. It has a function to make it. In a display mode in which many rod-like liquid crystal molecules in the liquid crystal cell are aligned substantially horizontally (eg, STN), the liquid crystal molecules of the optically anisotropic layer have a function of aligning substantially vertically. . In a display mode in which many rod-like liquid crystal molecules in the liquid crystal cell are substantially obliquely aligned (for example, TN), the liquid crystal molecules of the optically anisotropic layer have a function of substantially obliquely aligning. .

Specific types of polymers used in the alignment film of the present invention are described in the literature on optical compensation sheets 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 No. [0022] in JP-A-8-338913. Preferable examples include water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol). Among these, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol. Polyvinyl alcohol is most preferred.

  The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%, and most preferably 85 to 95%. The degree of polymerization of polyvinyl alcohol is preferably 100 to 3000.

  The modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of 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 atoms 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] in JP-A 2000-56310, paragraph numbers [0022] to [0145] in JP-A 2000-155216, Examples described in Paragraph Nos. [0018] to [0022] in the specification of JP-A-2002-62426.

[Curing compound]
In the present invention, the composition for forming an alignment film comprises two or more aldehydes as a curing compound for curing a polymer (preferably a water-soluble polymer, more preferably polyvinyl alcohol or modified polyvinyl alcohol) used for the alignment film. Contains aldehyde compounds containing groups. Specific examples of the compound include glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, pimeroaldehyde, suberoaldehyde, azelaldehyde, sebacoaldehyde, asparaldehyde, 1,2,4-butanetri Carbaldehyde, 3-formylhexane dial, cyclohexane dicarbaldehyde, cyclohexane diacetaldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, benzenetrialdehyde, 1,4,5,8-naphthalenetetraacetaldehyde, both terminal aldehyded povalaldehyde, Examples include dialdehyde starch. The aldehyde compound used in the present invention is not limited to these.
Among these, a highly reactive bifunctional (two aldehyde groups) aliphatic aldehyde compound is particularly preferable.
Moreover, you may use together a conventionally well-known crosslinking agent as a curable compound provided. Examples thereof include N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, and isoxazoles. Specific examples include compounds described in paragraphs [0023] to [0024] in JP-A-2002-62426.
When these crosslinking agents are used in combination, the content is preferably 30% by weight or less, more preferably 10% by weight or less in the total curable compound.

  The addition amount of the curable compound is preferably from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, based on the polymer. The amount of the unreacted curable compound remaining in the alignment film is preferably 1.0% by weight or less, and more preferably 0.5% by weight or less. It is preferable that the curable compound remaining in the alignment film is 1.0% by weight or less because sufficient durability can be obtained. In addition, it is preferable to use such an alignment film in a liquid crystal display device because reticulation does not occur even if it is kept for a long time or left in a high temperature and high humidity atmosphere for a long time.

[Nucleophile contained in alignment film]
In the present invention, the alignment film composition is characterized in that it contains at least one nucleophilic agent having a nucleophilic constant (n _CH3I ) of 5 or more and 10 or less such as Pearson. The nucleophilic constant (n) of Pearson et al. Is preferably 6.5 or more and 10 or less, more preferably 7 or more and 10 or less (hereinafter, the nucleophilic constant (n _CH3I ) is changed to the nucleophilic constant (n). May be written). Here, the nucleophilic constant (n _CH3I ) of Pearson et al. G. Pearson, et al., J. MoI. Am. Chem. Soc. 89, 1827 (1967), and the contents described in Kunio Okamoto, "Lecture Organic Reaction Mechanism 3, Nucleophilic Substitution Reaction" pp147 (Tokyo Chemical Dojin (1970)) and the like. It is done. Examples of the nucleophilic reagent that provides the nucleophilic constant (n) include the following reagents (the numbers in parentheses indicate the nucleophilic constant (n)).
Organic bases (for example, triethylamine (6.66), diethylamine (7.00), N, N-dimethylcyclohexylamine (6.73), pyridine (5.23), pyrrolidine (7.23), piperidine (7. 30), aniline (5.70), N, N-dimethylaniline (5.64), etc.), NH ₃ (5.5), ArO ⁻ (Ar represents an aryl group, phenyl group, tolyl group, xylyl group) And methoxyphenyl group, for example, phenolate anion (5.75) and the like, hydroxylylamine (6.60), SCN ⁻ (6.70), thiourea (7.27), OH ⁻ (6 .58), I ⁻ (7.42), (R) ₃ P (R represents a hydrocarbon group or —OR ¹ group (R ¹ represents a hydrocarbon group). Examples of the hydrocarbon group include methyl group, ethyl group, Group, propyl group, butyl group, Hexyl group, phenyl group, tolyl group, etc. For example, triethylphosphine (8.72), tributylphosphine (8.69), triphenylphosphine (7.00), trimethoxyphosphine (5.00 ), Etc.), RS ⁻ (R represents a hydrocarbon group such as butyl group, hexyl group, octyl group, phenyl group, tolyl group, etc., phenylthiolate ion (9.92) etc.), SO ₃ ^2- (8.53), S ₂ O ₃ ²⁻ (8.95), and the like.
The anionic molecule mentioned as the nucleophile is used as a compound that forms a salt with an inorganic cation (“nucleophile” in the present invention). The inorganic cation is not particularly limited, but specifically, an ammonium cation, a metal cation (as the metal, any of alkali metal, alkaline earth metal, transition metal, etc. may be used. For example, Li, Na, K, Be, Mg, Ca, Ba, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Co, Cu, Ag, Zn, B, Al, etc.).
More preferably, an ammonium cation or a metal ion selected from Li, Na, K, Mg, Ca, Ba, Al, Ti, Zr, Co, Ni, and Zn can be used.
More preferably, a salt having good solubility in water / methanol is formed.
As a result, the coated surface of the optical compensation sheet obtained by applying an optically anisotropic layer after aligning the obtained alignment film by an aligning means is good and reduces or eliminates optical defects such as white spots. The improvement effect is expressed. The presumed reason is that the nucleophilic substance contained in the alignment film distributes the cross-linking agent contained in the alignment film stably and uniformly, so that when the optically anisotropic layer is applied, the alignment state of the liquid crystal molecules is changed. One factor seems to be to reduce the impact. Naturally, the effect varies depending on the amount added, so the timely amount needs to be adjusted.

  Particularly preferable nucleophiles of the present invention include sulfites (sodium salts, potassium salts, ammonium salts, etc.) that generate sulfite ions, and thiosulfates (sodium salts, potassium salts, ammonium salts, etc.) that generate thiosulfate ions. .

  As a method for preparing the coating solution for the alignment film, (a) a method in which a crosslinking agent and a nucleophile are separately added to a solution in which the alignment film material is dissolved, and (b) a solution of a high concentration crosslinking agent is prepared. And adding a nucleophile therein and adding the mixed solution to the solution in which the alignment film material is dissolved, (c) a high concentration crosslinking agent and nucleophile in the solution in which the alignment film material is dissolved. The method of adding the solution which added the mixed solution which melt | dissolved this is mentioned. The solution of a high concentration crosslinking agent is preferably a 10 to 50 wt% solution. In the present invention, the methods (b) to (c) are preferable.

  The alignment film is coated with a coating solution of an alignment film forming composition containing at least the polymer, an aldehyde compound (curable compound), and a nucleophile on a transparent support, and then dried by heating (crosslinked). It is a cured film that can be formed by orientation treatment. 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 should be a mixed solvent of an organic solvent (eg, methanol, ethanol, isopropanol, etc.) having a defoaming action and water. preferable. The ratio by weight of water: methanol is preferably 0: 100 to 99: 1, and more preferably 0: 100 to 91: 9. Thereby, generation | occurrence | production of a bubble is suppressed, Since the defect of the layer surface of an alignment film and also an optically anisotropic layer reduces remarkably, it is preferable.

(Amount of nucleophile added)
The addition amount of the nucleophile is preferably 0.001 to 1.0% by weight, more preferably 0.005 to 0.8% by weight, based on the polymer. It is preferable that the addition amount of the nucleophilic agent is within the above range because good alignment of the liquid crystal is obtained and alignment defects and liquid crystal domain unevenness do not occur.

[Method for forming alignment film]
The alignment film of the present invention is prepared by applying a coating solution of the alignment film composition as described above by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure, and die coating. (Extrusion coating method (US Pat. No. 2,681,294), slide coating method, extrusion coating method) can be used for coating. The coating method is described in various documents (for example, Modern Coating and Drying Technology, Edward Cohen and Edgar B. Gutoff, Edits., VCH Publishers, Inc, 1992). A rod coater method, a gravure coater method, a blade coater method, and a die coater method that can be stably operated even in a small coating amount range are preferable.
In particular, the rod coater method or the die coater method is preferable. Furthermore, the novel die coater method described below, which is a non-contact method between the coating device portion and the coating support surface, which can be applied at a high speed without causing uneven coating stripes in a small coating amount region, is preferable.

(Die coater method)
As a preferred embodiment of the die coater, a method of applying the coating liquid from the slot of the tip lip by bringing the land of the tip lip of the slot die close to the surface of the transparent support that is continuously supported by the backup roll, When the slot die having a land length in the web traveling direction of the tip lip on the transparent support traveling direction side of the slot die is set to 30 μm or more and 100 μm or less and the slot die is set at a coating position, the progress of the web There is a method in which the gap between the tip lip and the web opposite to the direction is applied using a coating apparatus installed so that the gap between the tip lip and the web on the web traveling direction side is 30 μm or more and 120 μm or less. It is done.
This is preferable because the coating solution of the low-concentration, low-viscosity curable composition of the present invention can be accurately and stably applied in an extremely small amount.

(Die coater configuration)
A cross-sectional view of a coater using a slot die embodying the present invention is shown in FIG. The coater 10 is applied to the web 12 supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web 12.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be, for example, a substantially circular shape as shown in FIG. 1 or a semicircular shape. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web 12, and has a cross-sectional shape in the width direction of the slot die 13 like the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

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

FIG. 2 shows a cross-sectional shape of the slot die 13 in comparison with a conventional one, (A) shows the slot die 13 of the present invention, and (B) shows a conventional slot die 30. In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 of the present invention, the land length I _LO of the downstream lip land is shortened, so that application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is preferably 30 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, and further preferably 30 μm or more and 60 μm or less. When the land length I _LO of the downstream lip is 30 μm or more, the edge or land of the tip lip is not chipped, no streak is generated in the coating film, and it can be preferably applied. Moreover, it is preferable because the setting of the wet line position on the downstream side is easy and the coating liquid does not easily spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, if the land length I _LO of the downstream lip is 100 μm or less, beats can be formed and thin layer coating can be performed, which is preferable.

Further, the downstream lip land 18b has an overbite shape closer to the web 12 than the upstream lip land 18a. Therefore, the degree of decompression can be lowered, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream lip land 18b and the web 12 of the upstream lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web 12 indicates the gap between the downstream lip land 18 b and the web 12.

FIG. 3 is a perspective view showing a slot die and its periphery in a coating process in which the present invention is implemented. On the opposite side of the web 12 from the direction of travel, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression adjustment can be performed. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps G _B and G between the back plate 40a and the web 12 and between the side plate 40b and the web 12, respectively. _S exists. 4 and 5 are cross-sectional views showing the decompression chamber 40 and the web 12 that are close to each other. The side plate and the back plate may be integrated with the chamber body as shown in FIG. 4, or may be structured such that the gap is appropriately changed as shown in FIG. In any structure, the gaps between the back plate 40a and the web 12 and between the side plate 40b and the web 12 are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web 12 of the decompression chamber 40, when the vacuum chamber 40 is installed beneath the web 12 and the slot die 13 as shown in FIG. 3, the uppermost end of the back plate 40a to the web 12 Indicates the gap.

Is preferably installed to be larger than the gap G _L between the back plate 40a and the end lip 17 and the web 12 of the slot die 13 the gap G _B of the web 12, the bead vicinity due to the eccentricity of the backup roll 11 thereby The change in the degree of decompression can be suppressed. For example, when the gap G _L between the end lip 17 and the web 12 of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web 12 is preferably 100μm or 500μm or less.

(Material, accuracy)
The longer the length of the tip lip on the traveling direction side of the web in the web traveling direction, the more disadvantageous it is for bead formation.If this length varies between arbitrary locations in the slot die width direction, It becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.
Further, if the material of the tip end lip of the slot die is made of a material such as stainless steel, the length of the slot die tip lip in the web running direction is 30 μm to 100 μm as described above. Even within this range, the accuracy of the tip lip cannot be satisfied. Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.

In order to realize high-precision coating, the length of the land on the web traveling direction side of the tip lip and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of these two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness of the tip lip and the backup roll is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.
When applying, two or more layers may be applied simultaneously. Examples of the simultaneous application method include those described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973). .
The film thickness after drying is preferably 0.1 to 10 μm. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form a sufficient crosslink, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes.

Furthermore, when the coating liquid for the optically anisotropic layer is applied after the coating liquid of the composition for forming an alignment film of the present invention is applied to a support, dried and aligned by an aligning means, It is preferable that the surface be kept in the range of pH 4.0 to 10.0. Furthermore, pH 4.5-8.0 is more preferable.
Further, when applying the coating solution 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, ΔpH is in the range of ± 0.15.
When the pH fluctuation range is in the above range, the optical compensation sheet provided with the optically anisotropic layer is preferable because optical defects are further reduced.

The method for measuring the pH value of the alignment film surface is to leave the sample coated with the alignment film in an environment of (temperature 25 ° C./humidity 65% RH) for 1 day, and then place 10 ml of pure water in a nitrogen atmosphere. Immediately read the pH value with a pH meter.
Specifying the pH value of the alignment film surface of the present invention and controlling ΔpH in the coating width direction can be achieved by coating by the rod coater method or the dar coater method. Furthermore, it is also effective to adjust the drying temperature of the film surface, the air volume when using the drying air, the wind direction, and the like.

The alignment film is provided on the transparent support or the undercoat layer. The alignment film can be formed by rubbing the surface after crosslinking the polymer layer as described above.
For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of the LCD can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.
In the case of photo-alignment by light irradiation, the light source as the light irradiation device can be an ultra-high pressure mercury lamp, xenon lamp, fluorescent lamp, laser, etc. Are combined with a polarizing film (through the polarizing film) to convert the ultraviolet light into linearly polarized light and irradiate the photo-alignment film. As the polarizing film, stretch dyed PVA is mainly used. As this linearly polarized ultraviolet irradiation device, for example, the one disclosed in JP-A-10-90684 can be used.
The thickness of the alignment film is preferably 0.01 to 5 μm, and more preferably 0.05 to 1 μm.

[Optically anisotropic layer]
The optically anisotropic layer of the present invention is formed from liquid crystalline molecules.
As the liquid crystal molecules, rod-like liquid crystal molecules or discotic liquid crystal molecules are preferable.
Examples of rod-like liquid crystalline molecules 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 compounds are described in, for example, the Chemistry of the Chemical Society of Japan, Vol. 22, Chapter 4, Chapter 7 and Chapter 11 of Liquid Crystal Chemistry (1994), and the 142nd Committee of the Japan Society for the Promotion of Science. Examples include compounds described in literature such as Chapter 3. These low-molecular liquid crystal compounds preferably have a polymerizable group in the molecule (for example, paragraph number [0016] of JP 2000-304932 A, paragraph number [0055] of JP 2002-6138 A, etc.) Description). In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used. The high molecular liquid crystalline molecule is a polymer having a side chain corresponding to the above low molecular liquid crystalline molecule. Examples of the optical compensation sheet using polymer liquid crystalline molecules include compounds described in JP-A-5-53016.

Examples of discotic liquid crystalline molecules include various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); , Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem., Vol. 96, 70 (1984); JM Lehn et al., J. Chem. Soc., Chem. Comm., Page 1794 (1985); J. Zhang et al., J. Am. Chem. Soc., Vol. 116, page 2655 (1994)). As for the polymerization of discotic liquid crystalline molecules, the description in JP-A-8-27284 can be mentioned.
In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. A compound in which the discotic core and the polymerizable group are bonded via a linking group is preferable, whereby the alignment state can be maintained even in the polymerization reaction. Examples thereof include compounds described in paragraph numbers [0151] to [0168] in JP-A 2000-155216.
In order to optically compensate a liquid crystal cell in which rod-like liquid crystalline molecules such as STN mode are twisted, it is preferable that the discotic liquid crystalline molecules are also twisted. When an asymmetric carbon atom is introduced into the linking group, the discotic liquid crystal molecules can be twisted and aligned in a spiral shape. Further, even when an optically active compound containing an asymmetric carbon atom (chiral agent) is added to the optically anisotropic layer, the discotic liquid crystalline molecules can be twisted and aligned in a helical manner.

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

[Other components of optically anisotropic layer]
Along with the liquid crystal molecules described above, a plastic film, a surfactant, a polymer containing a fluoroaliphatic group, a polymerizable monomer, a polymer, an aligning agent, a tilt angle controlling agent, etc. are used in combination to form a uniform coating film. Properties, film strength, orientation of liquid crystal molecules, and the like can be improved. It is preferable that the liquid crystal molecules have compatibility with the liquid crystal molecules and can change the tilt angle of the liquid crystal molecules or do not inhibit the alignment.

  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 above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in paragraph numbers [0018] to [0020] in JP-A No. 2002-296423. The amount of the compound added is generally in the range of 1 to 50% by weight and preferably in the range of 5 to 30% by weight with respect to the discotic liquid crystalline molecules.

Examples of the surfactant include conventionally known compounds, and a fluorine-containing surfactant is particularly preferable. Specific examples include compounds described in paragraph numbers [0028] to [0056] in JP-A-2001-330725.
The polymer used together with the discotic liquid crystalline molecules is preferably capable of changing the tilt angle of the discotic liquid crystalline molecules. Specifically, for example, compounds described in paragraphs [0036] to [0094] in JP-A No. 2004-139015 and paragraphs [0029] to [0058] in JP-A No. 2004-101820 are described. Can be mentioned.
A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph [0178] of JP-A No. 2000-155216. The addition amount of the polymer is preferably in the range of 0.1 to 10% by weight, and preferably in the range of 0.1 to 8% by weight with respect to the liquid crystal molecules so as not to disturb the alignment of the liquid crystal molecules. It is more preferable.
The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline molecule is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.
It is also possible to use an optically anisotropic layer described in Japanese Patent No. 2004-139015 using the above compound.

  The polymer containing a fluoroaliphatic group (hereinafter referred to as “polymer A”) is a copolymer containing a repeating unit derived from a fluoroaliphatic group-containing monomer and a repeating unit represented by the following general formula (1). Polymers are preferred.

上記一般式（１）についての詳細な説明は、後で述べる。

Detailed description of the general formula (1) will be given later.

First, the polymer (polymer A) containing a fluoroaliphatic group will be described below.
The repeating unit derived from the fluoroaliphatic group-containing monomer contained in the polymer A is preferably a polymer having a fluoroaliphatic group in the side chain. The fluoroaliphatic group preferably has 1 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aliphatic group may be linear or cyclic, and when it is linear, it may be linear or branched. Of these, a linear fluoroaliphatic group having 6 to 10 carbon atoms is preferable. The degree of substitution with fluorine atoms is not particularly limited, but 50% or more of hydrogen atoms in the aliphatic group are preferably substituted with fluorine atoms, and more preferably 60% or more are substituted. The fluoroaliphatic group is contained in a side chain bonded to the polymer main chain via an ester bond, an amide bond, an imide bond, a urethane bond, a urea bond, an ether bond, a thioether bond, an aromatic ring, or the like. Specific examples of the fluoroaliphatic group-containing monomer contained in the polymer A are given below, but the present invention is not limited to the following specific examples.

  Next, the repeating unit represented by the general formula (1) will be described below.

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

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

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

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

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

L represents a divalent linking group selected from the above linking group group, or a divalent linking group formed by combining two or more thereof. In the linking group group, R ^{4 in} —NR ⁴ — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom or an alkyl group. R ⁵ in —PO (OR ⁵ ) — represents an alkyl group, an aryl group or an aralkyl group, and preferably an alkyl group. When R ⁴ and R ⁵ represent an alkyl group, an aryl group or an aralkyl group, the number of carbon atoms is the same as that described in the “substituent group”. L preferably contains a single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, an alkylene group or an arylene group, and is a single bond, —CO—, —O—. , —NR ⁴ —, an alkylene group or an arylene group is particularly preferable, and a single bond is most preferable. When L contains an alkylene group, the carbon number of the alkylene group is preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6. Specific examples of particularly preferred alkylene groups include methylene, ethylene, trimethylene, tetrabutylene, hexamethylene groups and the like. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene and naphthalene groups. When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 36, more preferably 7 to 26, and particularly preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group. The group listed as L may have a suitable substituent. Examples of such a substituent include those similar to the substituents exemplified above as the substituents for R ^{1 to} R ³ .
Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

As the solvent used for preparing the coating liquid for the optically anisotropic layer, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide, acetamide, etc.), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, tetrahydrofuran, trioxane, 1,3-dioxolane, etc.), hydrocarbons (Eg, benzene, toluene, hexane, cyclohexane, etc.), alkyl halides (eg, chloroform, dichloromethane, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone, methyl propyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.), ethers (eg, 1,2-dimethoxyethane, 1,3-dimethoxypropane, etc.), alcohols (eg, methanol, ethanol, propanol, ethylene glycol, propane glycol, etc.). Of these, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
The coating solution can be applied by a known method (eg, rod coating method, direct gravure coating method, reverse gravure coating method, die coating method (extrusion coating method, extrusion method, slide coating method, slit coating method)). .

Examples of the aligning agent include substances having the following structures.
Formula (I)
Z- (XQ) _m
In the formula, Z represents an m-valent linking group. m represents an integer of 2 or more. X represents NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, or S, and a plurality of X may be the same or different. Q represents a hetero ring or an aromatic ring, and a plurality of Q may be the same or different.

  In the general formula (I), Z represents an m-valent linking group. Z is preferably a linking group other than an aromatic ring.

  In the general formula (I), Q represents a heterocycle or an aromatic ring, and a plurality of Q may be the same or different. Examples of the heterocyclic ring are 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic ring, and preferably the ring-constituting atoms are carbon atoms, A heterocycle selected from a nitrogen atom and a sulfur atom and having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- to 6-membered aromatic having 3 to 30 carbon atoms Of the heterocycle. Examples of the aromatic ring are 6 to 30 membered substituted or unsubstituted aromatic rings, preferably 5 or 6 membered substituted or unsubstituted aromatic ring groups, and more preferably a heterocyclic aromatic ring. is there.

  Examples of the substituent that Q may have include an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, and n-propyl. , Isopropyl, t-butyl, n-octyl, dodecyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, 2-hexyldecyl, 2-octyldodecyl, 3- (2,4-di-t-amylphenoxy Propyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, and a multicycloalkyl group such as bicyclo An alkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms; Examples thereof include groups having a polycyclic structure such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl) and tricycloalkyl groups. A monocyclic cycloalkyl group is particularly preferred).

  An alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably Examples of the substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and include polycycloalkenyl groups such as bicycloalkenyl groups (preferably A substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-ene -4-yl), tricycloalkenyl groups, and monocyclic cycloalkenyl groups are particularly preferred.), Alkynyl groups (preferably Substituted or unsubstituted alkynyl group prime 2-30, for example, ethynyl, propargyl, trimethylsilylethynyl group),

  Aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, o-2- (perfluorohexyl) Ethoxyphenyl, o-3- (perfluorohexyl) propyloxyphenyl, o-2- (6H-dodecafluorohexyl) ethoxyphenyl, o- (8H-hexadecafluorooctyl) methoxyphenyl), heterocyclic group (preferably 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, and more preferably the ring-constituting atoms are carbon atom, nitrogen atom and sulfur atom And at least a heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy, 1H, 1H, 9H- Hexadecafluorononanoxy, 2-perfluorohexylethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy, 2-methylphenoxy, 2,4- Di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy, o-2- (perfluorohexyl) ethoxyphenoxy, o-3- (perfluorohexyl) propyloxy Phenoxy, o-2- (6H-dodecafluorohexyl) ethoxy Phenoxy, o- (8H-hexadecafluorooctyl) methoxyphenoxy), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy group ( Preferably, it is a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and the heterocyclic portion is preferably a heterocyclic portion described for the aforementioned heterocyclic group, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, 3-perfluorohexylpropylamino, 3- (2,4-di-t-amylphenoxy) propylamino, 3- (2-ethylhexyloxy) propylamino, 3- (2-hexyldecanooxy) propylamino, 3-dodecyloxypropylamino, 3- (3-perfluorohexylpropyloxy) propylamino, 3- (3- (6H-perfluorohexyl) propyloxy) propylamino, Anilino, N-methylanilino, diphenylamino, 2-methyloxyanilino, 2- ( -Perfluorohexylpropyloxy) anilino, 2- (2-perfluorobutylethyloxy) anilino, 2,4-di (2-perfluorohexylethyloxy) anilino, 2- (6H-perfluorohexylmethyloxy) anilino 3,4-di (3-perfluorohexylpropyloxy) anilino, N-1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, a C 1-30 substituent or An unsubstituted alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri- n-octyloxyphenylcarbonylamino), a Nocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino) An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methyl Sulfonylami , Butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Base Yes, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms) And, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), halogen atom (for example, chlorine atom, bromine atom, iodine atom),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenylazo, p Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide and N-phthalimide) A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably substituted having 2 to 30 carbon atoms) Or an unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include alkylcarbonylaminosulfonyl group, arylcarbonylaminosulfonyl group, alkylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, specifically methylsulfonylaminocarbonyl, p-methyl. Examples include phenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  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.

  Further, the molecules may be linked by a substituent, and the general formula (I) may be a multimer (for example, a dimer, a trimer, etc.). Among the multimers, dimers, trimers, or tetramers are preferred.

  The general formula (I) is more preferably the following general formula (III).

式中、Ｚはｍ価の連結基をあらわす。ｑは２以上の整数を表す。ＸはＮＲａ（Ｒａは水素原子、アルキル基またはアリール基を表す）、Ｏ、Ｓのいずれかをあらわし、複数のＸは同じでも異なっても良い。Ｒ及びＲ’は置換基をあらわし、同じでも異なっていてもよく、複数のＲ及びＲ’はそれぞれ同じでも異なっていてもよい。

In the formula, Z represents an m-valent linking group. q represents an integer of 2 or more. X represents NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, or S, and a plurality of X may be the same or different. R and R ′ represent a substituent, which may be the same or different, and a plurality of R and R ′ may be the same or different.

  In the general formula (III), examples of the substituent represented by R and R ′ include the substituents that Q may have in the general formula (I).

  Examples of the substituent for R and R ′ include those represented by the following general formula (VIII). That is, the general formula (III) includes multimers (eg, dimers, trimers, etc.).

式中、Ｚ¹はｍ価の連結基をあらわす。ｑは２以上の整数を表す。Ｘ¹及びＸ²はＮＲａ（Ｒａは水素原子、アルキル基またはアリール基を表す）、Ｏ、Ｓのいずれかをあらわし、複数のＸ¹及びＸ²はそれぞれ同じでも異なっても良い。Ｒ¹及びＲ²は置換基をあらわし、同じでも異なっていても良く、複数のＲ¹及びＲ²はそれぞれ同じでも異なっていてもよい。

In the formula, Z ¹ represents an m-valent linking group. q represents an integer of 2 or more. X ¹ and X ² represent NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, or S, and a plurality of X ¹ and X ² may be the same or different. R ¹ and R ² represent a substituent, and may be the same or different, and a plurality of R ¹ and R ² may be the same or different.

In the general formula (VIII), examples of the substituent represented by R ¹ and R ² include the substituents that Q may have in the general formula (I).
Next, the following general formula (IV) will be described.

式中、Ｚ¹¹は二価の連結基をあらわす。Ｘ¹¹及びＸ¹²はＮＲａ（Ｒａは水素原子、アルキル基またはアリール基を表す）、Ｏ、Ｓのいずれかをあらわし、同じでも異なっても良い。Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＲ¹⁴は置換基をあらわし、それぞれ同じでも異なっていても良い。

In the formula, Z ¹¹ represents a divalent linking group. X ¹¹ and X ¹² represent NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, and S, and may be the same or different. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a substituent, and may be the same or different.

In the general formula (IV), the divalent linking group represented by Z ¹¹ is an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —O—, —CO—, — A divalent linking group selected from the group consisting of SO—, —SO ₂ — and combinations thereof is preferable.

In the general formula (IV), examples of the substituents represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are those exemplified as the substituents for R and R ′ in the general formula (III). Can be mentioned.

Preferably, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each an optionally substituted alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkyl group An amino group, an arylamino group, a heterocyclic amino group, and more preferably an alkylamino group which may have a substituent [for example, methylamino, dimethylamino, 3-perfluorohexylpropylamino, 3- (2,4 -Di-t-amylphenoxy) propylamino, 3- (2-ethylhexyloxy) propylamino, 3- (2-hexyldecanooxy) propylamino, 3-octyloxypropylamino, 3-dodecyloxypropylamino, 3 -(3-perfluorohexylpropyloxy) propylamino, 3- (3- (6H-perful Rohexyl) propyloxy) propylamino], arylamino groups [eg anilino, N-methylanilino, diphenylamino, 2-methyloxyanilino, 2- (3-perfluorohexylpropyloxy) anilino, 2- (2-perfluoro Butylethyloxy) anilino, 2,4-di (2-perfluorohexylethyloxy) anilino, 2- (6H-perfluorohexylmethyloxy) anilino, 3,4-di (3-perfluorohexylpropyloxy) anilino ]. Examples of the substituent which may be included include those exemplified as the substituents for R and R ′ described above.
More preferably, the general formula (IV) is the following general formula (IX).

式中、Ｘ⁵¹及びＸ⁵²はＮＲａ（Ｒａは水素原子、アルキル基またはアリール基を表す）、Ｏ、Ｓのいずれかをあらわし、同じでも異なっても良い。Ａ⁵¹、Ａ⁵²及びＡ⁵³は２価の連結基を表し、同じでも異なっても良く、複数のＡ⁵²は同じでも異なってもよい。ｔは０以上の整数を表す。Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＲ⁵⁴は置換基をあらわし、同じでも異なっていても良い。

In the formula, X ⁵¹ and X ⁵² represent NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, or S, and may be the same or different. A ⁵¹ , A ⁵² and A ⁵³ represent a divalent linking group and may be the same or different, and a plurality of A ⁵² may be the same or different. t represents an integer of 0 or more. R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ represent a substituent and may be the same or different.

In the general formula (IX), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are the same as those shown in the general formula (IV), and preferred ranges are also the same.

In the general formula (IX), A ⁵¹ , A ⁵² and A ⁵³ are divalent linking groups such as an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, A divalent linking group selected from the group consisting of —SO—, —SO ₂ — and combinations thereof is preferable. More preferably, it is an alkylene group (a linear or branched substituted or unsubstituted alkylene group, preferably an alkylene group having 1 to 30 carbon atoms, such as —CH ₂ —, — (CH ₂ ) ₂ —, —CH _2. CH (CH ₃ ) —, —CH ₂ C (CH ₃ ) ₂ —, — (CH ₂ ) ₄ —), and more preferably — (CH ₂ ) ₂ —, —CH ₂ CH (CH ₃ ) —. , — (CH ₂ ) ₄ —.

  The aforementioned alkylene group, alkenylene group, divalent aromatic group and divalent heterocyclic residue may have a substituent if possible, and examples of the substituent which may have include the aforementioned R and Examples listed as the substituent for R ′ are given.

  Next, the following general formula (V) will be described.

式中、Ｚ²¹、Ｚ²²及びＺ²³は二価の連結基をあらわし、それぞれ同じでも異なっても良い。Ｘ²¹〜Ｘ²⁶はＮＲａ（Ｒａは水素原子、アルキル基またはアリール基を表す）、Ｏ、Ｓのいずれかをあらわし、それぞれ同じでも異なっても良い。Ｒ²¹〜Ｒ²⁶は置換基をあらわし、それぞれ同じでも異なっていても良い。

In the formula, Z ²¹ , Z ²² and Z ²³ represent a divalent linking group, and may be the same or different. X ^{21 to} X ²⁶ represent NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, or S, and may be the same or different. R ^{21 to} R ²⁶ represent substituents, and may be the same or different.

In the general formula (V), Z ^{21 to} Z ²³ and R ^{21 to} R ²⁶ are the same as Z ¹¹ and R ^{11 to} R ¹⁴ shown in the general formula (IV), respectively, and preferable ranges thereof are also the same. .

  More preferably, the general formula (V) is the following general formula (X).

式中、Ｘ⁶¹〜Ｘ⁶⁶はＮＲａ（Ｒａは水素原子、アルキル基またはアリール基を表す）、Ｏ、Ｓのいずれかをあらわし、同じでも異なっても良い。Ａ⁶¹〜Ａ⁶⁹は２価の連結基を表し、同じでも異なっても良く、複数のＡ⁶²、Ａ⁶⁵、Ａ⁶⁸はそれぞれ同じでも異なってもよい。ｎ１〜ｎ３は０以上の整数を表す。Ｒ⁶¹〜Ｒ⁶⁶は置換基をあらわし、同じでも異なっていても良い。

In the formula, X ^{61 to} X ⁶⁶ represent NRa (Ra represents a hydrogen atom, an alkyl group or an aryl group), O, and S, and may be the same or different. A ^{61 to} A ⁶⁹ represent a divalent linking group and may be the same or different, and a plurality of A ⁶² , A ⁶⁵ and A ⁶⁸ may be the same or different. n1 to n3 represent an integer of 0 or more. R ^{61 to} R ⁶⁶ represent a substituent, and may be the same or different.

In the general formula (X), R ^{61 to} R ⁶⁶ are the same type as R ^{11 to} R ¹⁴ shown in the general formula (IV), and preferable ranges thereof are also the same.

In the general formula (X), A ^{61 to} A ⁶⁹ are divalent linking groups such as an alkylene group, alkenylene group, divalent aromatic group, divalent heterocyclic residue, —CO—, —SO—. , -SO ₂ - is preferably a and divalent linking group selected from the group consisting of. More preferably, it is an alkylene group (a linear or branched substituted or unsubstituted alkylene group, preferably an alkylene group having 1 to 30 carbon atoms, such as —CH ₂ —, — (CH ₂ ) ₂ —, —CH _2. CH (CH ₃ ) —, —CH ₂ C (CH ₃ ) ₂ —, — (CH ₂ ) ₄ —), and more preferably — (CH ₂ ) ₂ —, —CH ₂ CH (CH ₃ ) —. , — (CH ₂ ) ₄ —.

  The aforementioned alkylene group, alkenylene group, divalent aromatic group and divalent heterocyclic residue may have a substituent if possible, and examples of the substituent which may have include the aforementioned R and Examples listed as the substituent for R ′ are given.

  Preferred specific examples of the compounds represented by the general formulas (I), (III), (IV), (V), (IX) and (X) are shown below, but the compounds used in the present invention are not limited thereto. It is not limited. The compounds represented by the general formulas (I), (III), (IV), (V), (IX) and (X) have a polymerizable group as a substituent in order to fix the alignment state. You may have. Hereinafter, exemplary compounds (I-1) to (I-52) are shown.

  The compounds represented by the general formulas (I), (III), (IV), (V), (IX) and (X) may be used alone or in combination of two or more. . The amount of the compound added is preferably 0.01 to 20% by weight, particularly preferably 0.05 to 10% by weight, and most preferably 0.05 to 5% by weight based on the amount of the liquid crystal compound.

Examples of the tilt angle controlling agent include the following compounds.
Formula (II)
_{(Rf-Y-) n Ar (} -W) p
In the formula, Ar represents an aromatic heterocycle or an aromatic hydrocarbon ring, Y represents a single bond or a divalent linking group, Rf represents an alkyl group substituted with a fluorine atom, W represents a sulfo group or a carboxyl group Represents a group, n represents an integer of 1 to 4, and p represents 1 or 2. However, in Rf, the number of carbon atoms substituted with a fluorine atom is 1 to 4.

  More specifically, in the general formula (II), the aromatic heterocycle represented by Ar is preferably an aromatic heterocycle having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, such as a nitrogen atom. A hetero ring having a hetero atom such as an oxygen atom or a sulfur atom, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an isoxazole ring, a pyridine ring, a pyrimidine ring, a 1,3,5-triazine ring, an indole ring, Indazole ring, quinoline ring and carbazole ring are preferred. The aromatic hydrocarbon ring represented by Ar is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and most preferably a benzene ring. Ar is preferably an aromatic hydrocarbon ring.

The aromatic heterocycle or aromatic hydrocarbon ring represented by Ar may have a substituent, and examples of the substituent include the following groups.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, Particularly preferred are alkenyl groups having 2 to 8 carbon atoms, such as vinyl group, aryl group, 2-butenyl group and 3-pentenyl group), alkynyl groups (preferably having 2 to 20 carbon atoms, more preferred). Is an alkynyl group having 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl group and 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, and a naphthyl group. A substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms. Group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.),

  An alkoxy group (preferably having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group or a butoxy group), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, Particularly preferably, it is 2 to 10, for example, methoxycarbonyl group, ethoxycarbonyl group and the like, acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms). For example, an acetoxy group, a benzoyloxy group, etc.), an acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms). Acetylamino group, benzoylamino group, etc.), alkoxycarbonylamino group ( Preferably an alkoxycarbonylamino group 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), aryloxycarbonylamino A group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group), a sulfonyl An amino group (preferably a sulfonylamino group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably A sulfamoyl group having a prime number of 0 to 16, particularly preferably 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group), a carbamoyl group ( Preferably it is C1-C20, More preferably, it is C1-C16, Most preferably, it is C1-C12 carbamoyl group, for example, unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group Etc.),

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

  The substituent of the aromatic heterocycle or aromatic hydrocarbon ring represented by Ar is preferably an alkyl group, aryl group, alkoxy group, alkoxycarbonyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group. Particularly preferred are an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an acyloxy group, and most preferred is an unsubstituted aromatic heterocyclic ring or an aromatic hydrocarbon ring.

Y represents a divalent linking group or a single bond. In the case of a divalent linking group, an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, -CO-, -NR ^a- (R ^a has 1 to 5 is a divalent linking group selected from the group consisting of —O—, —S—, —SO—, —SO ₂ — and combinations thereof. The divalent linking group is a group obtained by combining at least two divalent linking groups selected from an alkylene group, —CO—, —NR ^a —, —O—, —S—, —SO ₂ — and a group thereof. It is more preferable that The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms in the arylene group is preferably 6-10. If possible, the alkylene group, alkenylene group and arylene group may be substituted by a group exemplified as the substituent of the aforementioned Ar (eg, alkyl group, halogen atom, cyano group, alkoxy group, acyloxy group, etc.). Good.
Y is preferably a divalent linking group, and particularly preferably a divalent linking group selected from the group consisting of an alkylene group, —O—, —S—, and combinations thereof.

The alkyl group substituted with a fluorine atom represented by Rf may have a cyclic structure or a branched structure. The substitution rate of fluorine atoms is preferably such that 50% or more of hydrogen atoms contained in the alkyl group are substituted with fluorine atoms, and more preferably 60% or more are substituted. However, the number of carbon atoms substituted with fluorine atoms is any one of 1-4. Rf is preferably terminated with a CF ₃ group or a CF ₂ H group, and particularly preferably a CF ₃ group. If possible, the alkyl group substituted with a fluorine atom represented by Rf is, if possible, a group exemplified as the substituent of Ar described above (eg, alkyl group, halogen atom, cyano group, alkoxy group, acyloxy group, etc.). May be substituted.

Specific examples of Rf are shown below.
_{Rf1: n-C 4 F 9} -
Rf2: C ₂ F ₅ −
_{Rf3: n-C 4 F 9} - (CH 2) 2 -
_{Rf4: n-C 4 F 9} - (CH 2) 3 -
Rf5: C ₂ F ₅ — (CH ₂ ) ₂ —
_{Rf6: H- (CF 2) 4} -
_{Rf7: H- (CF 2) 4} - (CH 2) -

  W is preferably a sulfo group, n is preferably 1 or 2, and p is preferably 1.

  The general formula (II) is particularly preferably the following general formula (IIa).

式中、Ｙ²は単結合又は２価の連結基を表し、Ｒｆ²はフッ素原子で置換されたアルキル基を表す。但し、Ｒｆ²において、フッ素原子で置換された炭素原子の数は１〜４である。

In the formula, Y ² represents a single bond or a divalent linking group, and Rf ² represents an alkyl group substituted with a fluorine atom. However, the Rf ^2, the number of substituted carbon atoms with fluorine atoms is 1-4.

In the general formula (IIa), Y ² and Rf ² are the same meanings as Y and Rf in formula (II), preferable ranges are also the same.

  Specific examples of the compound represented by the general formula (II) are shown below, but the compound used in the present invention is not limited thereto.

  The compound represented by the general formula (II) can be easily synthesized by combining a general alkylation reaction of a hydroxy group and a sulfonation reaction of an aromatic compound.

  The addition amount of the compound represented by the general formula (II) is preferably 0.01 to 20% by weight, particularly preferably 0.05 to 10% by weight based on the amount of the liquid crystal compound, and 0.05 to 1% by weight is most preferred.

[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 liquid crystalline molecules are substantially uniformly formed by a polymerization reaction. Most preferably, it is fixed in an oriented state. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by weight, more preferably 0.5 to 5% by weight, based on the solid content of the coating solution.
Light irradiation for polymerization of discotic liquid crystalline molecules is preferably performed using ultraviolet rays.
The irradiation energy is preferably 20 mJ / cm ^{2 to} 50 J / 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.

The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 0.7 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 liquid crystalline molecules is controlled by the type of liquid crystalline molecules, the type of alignment film, and the use of additives (eg, plasticizers, polymers, surfactants) in the optically anisotropic layer. The

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

(Nucleophile in alignment film and liquid crystal tilt angle on alignment film side)
Increasing or decreasing the tilt angle of the liquid crystal can be controlled by the amount of the nucleophilic agent contained in the alignment film. The reason is presumed that there is a change in surface energy at a micro level because it is partially segregated on the surface of the alignment film. It seems that the tilt angle of the liquid crystal near the alignment film changes according to the change of the surface energy.

As described above, the optical compensation sheet of the present invention is manufactured. As described above, the optical compensation sheet of the present invention has a layer structure in which a transparent support that has been subjected to adhesion treatment in advance, an alignment film, and an optically anisotropic layer are laminated in this order.
The optical compensation sheet of the present invention exhibits its functions remarkably by being bonded to a polarizing plate or used as a protective film for a polarizing plate.
Hereinafter, the polarizing plate and its production will be described in detail.

[Transparent protective film of polarizing plate]
The polarizing plate of the present invention comprises a polarizing film and a transparent protective film. That the protective film is transparent means that the light transmittance is 80% or more. As the transparent protective film, generally, a cellulose ester film, preferably the cellulose acylate film is used. The thickness of the transparent protective film is preferably 20 to 200 μm, and more preferably 30 to 100 μm. Especially preferably, it is 30-80 micrometers. Usually, a transparent protective film is disposed on both sides of the polarizing film.

  In the present invention, it is preferable to use an optical compensation sheet on one side of the polarizing plate instead of the transparent protective film. That is, whether the optically anisotropic layer of the optical compensation sheet (the first optically anisotropic layer closest to the polarizing film when a plurality of optically anisotropic layers is provided) is directly formed from liquid crystalline molecules on the polarizing film. Alternatively, it is preferably formed from liquid crystalline molecules through an alignment film. Specifically, the optically anisotropic layer is formed by applying the coating liquid for the optically anisotropic layer as described above to the surface of the polarizing film. As a result, without using a transparent protective film between the polarizing film and the optically anisotropic layer, a thin polarizing plate with a small stress (strain x cross-sectional area x elastic modulus) associated with the dimensional change of the polarizing film is created. The When the polarizing plate according to the present invention is attached to a large liquid crystal display device, an image with high display quality is displayed without causing problems such as light leakage.

[Surface treatment of optical compensation sheet]
When the optical compensation sheet is used instead of the transparent protective film of the polarizing plate, adhesion between the optical compensation sheet and the transparent protective film of the polarizing plate becomes a problem. In the present invention, the adhesion between the optical compensation sheet and the polarizing film is improved by surface-treating the surface of the optical compensation sheet on the polarizing film side. As the surface treatment, corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, acid treatment or alkali treatment is performed.
Examples of the treatment method such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, ozone treatment, acid treatment, and alkali treatment include the contents described in pages 30 to 31 of the public technical number 2001-1745. Can be mentioned. In the present invention, it is preferable to perform an alkali treatment, and examples thereof include the same contents as described in the saponification treatment of the above-described film.

[Polarizing film]
The polarizing film used in the present invention is usually preferably a coating type polarizing film represented by Optiva Inc., or a polarizing film comprising a binder and iodine or a dichroic dye.
Iodine and dichroic dye in the polarizing film exhibit deflection performance by being oriented in the binder. It is preferable that the iodine and the dichroic dye are aligned along the binder molecule, or the dichroic dye is aligned in one direction by self-assembly such as liquid crystal.
At present, a commercially available polarizing film is produced by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath and allowing iodine or dichroic dye to penetrate into the binder. Is common.
The commercially available polarizing film has iodine or dichroic dye distributed about 4 μm (about 8 μm on both sides) from the polymer surface, and a thickness of at least 10 μm is necessary to obtain sufficient polarization performance. The penetrability can be controlled by the solution concentration of iodine or dichroic dye, the temperature of the bath, and the immersion time.
As described above, the lower limit of the binder thickness is preferably 10 μm. The upper limit of the thickness is preferably as thin as possible from the viewpoint of light leakage of the liquid crystal display device. It is preferably not more than a commercially available polarizing plate (about 30 μm), preferably 25 μm or less, and more preferably 20 μm or less. If it is 20 μm or less, the light leakage phenomenon is not observed with a 17-inch liquid crystal display device, which is preferable.

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

As the binder for the polarizing film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used. Examples of the polymer include the same polymers as those described in the alignment film.
Most preferred are polyvinyl alcohol and modified polyvinyl alcohol.
The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127.
Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

The addition amount of the crosslinking agent in the binder is preferably 0.1 to 20% by weight with respect to the binder. The orientation of the polarizing element and the moisture and heat resistance of the polarizing film are improved.
The alignment film contains a certain amount of a crosslinking agent that has not reacted even after the crosslinking reaction has been completed. However, the amount of the remaining crosslinking agent is preferably 1.0% by weight or less and more preferably 0.5% by weight or less in the alignment film. In this way, even if the polarizing film is incorporated in a liquid crystal display device and used for a long time or left in a high temperature and high humidity atmosphere for a long time, the degree of polarization does not decrease.
About a crosslinking agent, the description of US reissue patent 23297 is mentioned. Boron compounds (eg, boric acid, borax) can also be used as a crosslinking agent.

As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (eg, sulfo, amino, hydroxyl).
Examples of the dichroic dye include compounds described in JIII Journal of Technical Disclosure No. 2001-1745, page 58 (issued on March 15, 2001).

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

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

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

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

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

The transparent protective film is preferably disposed on the surface of the polarizing film opposite to the optically anisotropic layer (arrangement of optically anisotropic layer / polarizing film / transparent protective film).
It is also preferable that the transparent protective film is provided with an antireflection film having an outermost surface having antifouling properties and scratch resistance. Any conventionally known antireflection film can be used.

As described above, the polarizing plate of the present invention is produced.
The optical compensation sheet of the present invention or the polarizing plate using the optical compensation sheet is advantageously used for a liquid crystal display device, particularly a transmissive liquid crystal display device.
Hereinafter, a liquid crystal display device, particularly a transmissive liquid crystal display device and its manufacture will be described in detail.

[Liquid Crystal Display]
The transmissive 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 sheet is disposed between the liquid crystal cell and one polarizing plate, or two optical compensation sheets are disposed between the liquid crystal cell and both polarizing plates.
A preferred form of the optically anisotropic layer in each liquid crystal mode will be described below.
In a preferable form of the optically anisotropic layer in each liquid crystal mode, the optical compensation sheet of the present invention or the polarizing plate using the optical compensation sheet can be optically compensated advantageously.

(TN mode liquid crystal display)
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and many publications are cited. 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)
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. Examples of the liquid crystal display device using the bend alignment mode liquid crystal cell include devices 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. Therefore, 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 (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (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).

(IPS mode liquid crystal display)
In the IPS mode liquid crystal cell, the liquid crystal molecules are always rotated in a horizontal plane with respect to the substrate, and are aligned so as to have a slight angle with respect to the longitudinal direction of the electrode when no electric field is applied. When an electric field is applied, the liquid crystal molecules change direction in the direction of the electric field. The light transmittance can be changed by arranging the polarizing plates sandwiching the liquid crystal cell at a predetermined angle. As the liquid crystal molecules, nematic liquid crystal having a positive dielectric anisotropy Δε is used. The thickness (gap) of the liquid crystal layer is more than 2.8 μm and less than 4.5 μm. This is because when the retardation Δn · d is more than 0.25 μm and less than 0.32 μm, a transmittance characteristic having almost no wavelength dependency within the visible light range can be obtained. By combining the polarizing plates, the maximum transmittance can be obtained when the liquid crystal molecules are rotated 45 ° from the rubbing direction to the electric field direction. The thickness (gap) of the liquid crystal layer is controlled by polymer beads. Of course, the same gap can be obtained with glass beads, fibers, and resin columnar spacers. The liquid crystal molecules are not particularly limited as long as they are nematic liquid crystals. The larger the value of the dielectric anisotropy Δε, the lower the driving voltage, and the smaller the refractive index anisotropy Δn, the thicker the liquid crystal layer (gap), the shorter the liquid crystal sealing time, and the gap. Variation can be reduced.

(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.

[Polarizing plate with antireflection film]
The polarizing plate of the present invention is preferably formed by further providing an antireflection film on the surface of the protective film of the air side polarizing film. Thereby, the reflection of external light is remarkably reduced or eliminated, and a clear image display becomes possible. For example, the antireflection film may be directly provided on the protective film of the polarizing film, or an antireflection film having an antireflection film provided on the transparent support may be bonded to the polarizing film protective film. The former embodiment is preferred from the viewpoint of thinning the polarizing plate.

[Antireflection film]
In general, the antireflection film transparently supports a low refractive index layer which is also an antifouling layer, and at least one layer having a higher refractive index than that of the low refractive index layer (ie, a high refractive index layer and a medium refractive index layer). It is provided on the body.

  As a method for forming the antireflection film, a transparent thin film of inorganic compounds (metal oxides, etc.) having different refractive indexes is laminated to form a multilayer film; the thin film is formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method. Forming method: After forming a colloidal metal oxide particle film by a sol / gel method of a metal compound such as a metal alkoxide, post-treatment (ultraviolet irradiation: JP-A-9-157855, plasma treatment: JP-A-2002-327310) ) To form a thin film. Further, as a method for forming an antireflection film having high productivity, various proposals have been made such as a method for forming an antireflection film by laminating and coating a thin film composition in which inorganic particles are dispersed in a matrix. Moreover, the antireflection film which gave the anti-glare property in which the uppermost layer surface has the shape of a fine unevenness | corrugation is mentioned to the antireflection film by this application | coating.

(Configuration of coating type antireflection film)
An antireflection film consisting of at least a middle refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) on the transparent support is designed to have a refractive index that satisfies the following relationship. The
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.

  Further, a hard coat layer may be provided between the transparent support and the medium refractive index layer. Furthermore, it may consist of a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer. Examples thereof include JP-A-8-122504, JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-11706, and the like. Further, other functions may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (for example, JP-A-10-206603, JP-A-2002). -243906 publication etc.) etc. are mentioned.

  The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. The hardness of the surface of the antireflection film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K-5400.

(High refractive index layer and medium refractive index layer)
The antireflective film of the present invention has a high refractive index layer (high refractive index layer and medium refractive index layer) from a curable film containing at least inorganic fine particles having a high refractive index having an average particle size of 100 nm or less and a matrix binder. It is preferable to become.

(Inorganic compound fine particles)
The inorganic compound fine particles used for the high refractive index include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1.9 or more.

  Examples of these inorganic compounds include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms. , Zr, Al (preferably Co) at least one element selected from the group consisting of titanium fine particles (hereinafter referred to as “specific oxide”). May be referred to as “)”. The total content of contained elements is preferably 0.05 to 30% by weight with respect to Ti, more preferably 0.1 to 10% by weight, still more preferably 0.2 to 7% by weight, and particularly preferably 0.3 to 5% by weight, most preferably 0.5 to 3% by weight.

  Said contained element exists in the inside or surface of the inorganic fine particle which has titanium dioxide as a main component. More preferably, it is 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.

  As another preferable inorganic particle, a composite oxide of 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 and a titanium element is used. And the composite oxide is an inorganic fine particle doped with at least one metal ion selected from Co ions, Zr ions, and Al ions (sometimes referred to as “specific composite oxide”). Is mentioned. Here, Ta, Zr, In, Nd, Sb, Sn, and Bi are preferable as the metal element whose refractive index of the oxide is 1.95 or more. In particular, Ta, Zr, Sn, and Bi are preferable. The content of the metal ions doped in the composite oxide is preferably within a range not exceeding 25% by weight with respect to the total amount of metal [Ti + Met] constituting the composite oxide from the viewpoint of maintaining the refractive index. More preferably, it is 0.05-10 weight%, More preferably, it is 0.1-5 weight%, Most preferably, it is 0.3-3 weight%.

  The doped metal ion may exist in any form of metal ion or metal atom, and is appropriately present from the surface to the inside of the complex oxide. It is preferably present both on the surface and inside.

  In order to obtain such ultrafine particles of an inorganic compound, the surface of the particles is treated with a surface treatment agent (for example, silane coupling agents, etc .: JP-A Nos. 11-295503 and 11-153703, JP-A No. 2000-9908, anionic compound or organometallic coupling agent: Japanese Patent Application Laid-Open No. 2001-310432, etc., core / shell structure with high refractive index particles as a core (Japanese Patent Application Laid-Open No. 2001-166104, US Patent) 2003 / 0202137A1) and a combination of specific dispersants (for example, JP-A-11-153703, US Pat. No. 6,210,858B1, JP-A-2002-27776069, etc.).

(Matrix binder)
Examples of the material for forming the matrix of the high refractive index layer include conventionally known thermoplastic resins and curable resin films. Also, at least one selected from a polyvinyl compound-containing composition containing at least two radically polymerizable and / or cationically polymerizable groups, an organometallic compound containing a hydrolyzable group, and a partial condensate composition thereof. The composition is preferred. Examples thereof include compounds described in JP-A Nos. 2000-47004, 2001-315242, 2001-31871, and 2001-296401. Furthermore, colloidal metal oxides obtained from hydrolyzed condensates of metal alkoxides and curable films obtained from metal alkoxide compositions are also preferred. These are described in, for example, JP-A-2001-293818.

  The refractive index of the high refractive index layer is generally 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm. Further, 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.

(Low refractive index layer)
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 in the range of 1.20 to 1.55, and more preferably in the range of 1.30 to 1.50. The low refractive index layer is preferably constructed as an outermost layer having scratch resistance and antifouling properties. As a 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. More preferably, it is 1.36-1.47. The fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing fluorine atoms in the range of 35 to 80% by weight. Examples of such compounds include paragraphs [0018] to [0026] of JP-A-9-222503, paragraphs [0019] to [0030] of JP-A-11-38202, and JP-A-2001-2001. Examples include the compounds described in paragraph Nos. [0027] to [0028] of Japanese Patent No. 40284, JP-A 2000-284102, JP-A 2004-45462, and the like.

  The silicone compound is a compound having a polysiloxane structure, preferably containing a curable functional group or a polymerizable functional group in the polymer chain and having a crosslinked structure in the film. For example, reactive silicone {for example, “Silane Plain” manufactured by Chisso Co., Ltd.}, silanol group-containing polysiloxane at both ends (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 sol / gel cured film in which an organometallic compound such as a silane coupling agent and a silane coupling agent having a specific fluorine-containing hydrocarbon group are cured by a condensation reaction in the presence of a catalyst is also preferable. For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (Japanese Patent Laid-Open Nos. 58-142958, 58-147483, 58-147484, Japanese Patent Laid-Open Nos. 9-157582, 11) -106704), silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (Japanese Patent Application Laid-Open Nos. 2000-117902, 2001-48590, 2002) 53804), and the like.

  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 hollow inorganic fine particles preferably have a refractive index of usually 1.17 to 1.40, preferably 1.17 to 1.37, and more preferably 1.17 to 1.35. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell forming the hollow inorganic fine particles. The refractive index of the hollow inorganic fine 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 refractive index of these hollow inorganic fine particles can be measured with an Abbe refractometer [manufactured by Atago Co., Ltd.].

  The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape.

The porosity w of the hollow inorganic fine particles is calculated according to the following formula (3), where r _{i is} the radius of the cavity in the particle and r _o is the radius of the particle outer shell.
Formula (3): w = (r _i / r _o ) ³ × 100

  The porosity of the hollow inorganic fine particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60% from the viewpoint of the strength of the particles and the scratch resistance of the antireflection film surface. .

  The average particle diameter of the hollow inorganic fine particles in the low refractive index layer is preferably 30 to 100%, more preferably 35 to 80%, and particularly preferably 40 to 60% 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 to 100 nm, more preferably 35 to 80 nm, and particularly preferably 40 to 60 nm. When the average particle size is in the above range, the strength of the antireflection film is sufficiently expressed.

  Examples of other additives contained in the low refractive index layer include 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 outermost layer is further formed on the low refractive index 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.). Although it is good, it is preferably formed by a coating method 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 most 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 is provided on the surface of the transparent support (or protective film; the same applies hereinafter) in order to impart physical strength to the antireflection film. In particular, it is preferably provided 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, and 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 composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 00/46617.

  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 (described later) provided with particles having an average particle size of 0.2 to 10 μm to provide an antiglare function (antiglare function).

  The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm.

  The hardness of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K-5400. Further, the scratch resistance of the hard coat layer is preferably as the wear amount of the test piece coated with the hard coat layer before and after the test is smaller in the Taber test according to JIS K-5400.

(Forward scattering layer)
The forward scattering layer is provided in order to give a viewing angle improvement effect when the viewing angle is inclined in the vertical and horizontal directions when a polarizing plate using a protective film provided with an antireflection film is applied to a liquid crystal display device. . By dispersing fine particles having different refractive indexes in the hard coat layer, it can also serve as a hard coat function. As for the forward scattering layer, for example, Japanese Patent Application Laid-Open No. 11-38208 with a specific forward scattering coefficient, Japanese Patent Application Laid-Open No. 2000-199809 with a relative refractive index of a transparent resin and fine particles in a specific range, and a haze value of 40% or more. JP-A-2002-107512 and the like which are defined as follows.

  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 most 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 weight) to form a surface uneven film, and these shapes are maintained thereon. A method of providing a low refractive index layer (for example, JP 2000-281410 A, JP 2000-95893 A, JP 2001-100004 A, 2001-281407, etc.), an uppermost layer (antifouling layer) A method of physically transferring an uneven shape onto the surface after coating (for example, as an embossing method, described in JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401, etc.) And the like.

  Specific examples of the optical compensation sheet, polarizing plate and liquid crystal display device of the present invention will be described below, but the present invention is not limited to these.

[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 acetate solution.
<Cellulose acetate solution composition>
Cellulose acetate having a substitution degree of 2.85 (6-position substitution degree: 0.90) 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) ) 300 parts by weight Methanol (second solvent) 45 parts by weight Dye (360FP manufactured by Sumika Finechem Co., Ltd.) 0.0009 parts by weight

  In another mixing tank, 16 parts by weight of the following retardation increasing agent, 80 parts by weight of methylene chloride and 20 parts by weight of methanol were added and stirred while heating to prepare a retardation increasing agent solution.

上記組成のセルロースアセテート溶液４６４重量部にレターデーション上昇剤溶液３６重量部、およびシリカ微粒子“AEROSIL972”（商品名；日本アエロジル（株）製）１．１重量部を混合し、充分に攪拌してドープを調製した。

464 parts by weight of the cellulose acetate solution having the above composition was mixed with 36 parts by weight of the retardation increasing agent solution and 1.1 parts by weight of silica fine particles “AEROSIL972” (trade name; manufactured by Nippon Aerosil Co., Ltd.) and stirred thoroughly. A dope was prepared.

The obtained dope was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, peeled, and then dried with a cellulose acylate film CA-1 having a residual solvent amount of 0.3% by weight (thickness 100 μm). ) Was manufactured.
When the retardation of the produced cellulose acylate film CA-1 was measured, the retardation Rth in the thickness direction was 85 nm, and the in-plane retardation Re was 7 nm.

(Saponification treatment)
The cellulose acylate film (CA-1) is passed through a dielectric heating roll having a temperature of 60 ° C. and heated to a film surface temperature of 40 ° C., and then an alkali solution (S-1) having the composition shown below is applied to a rod coater. Was applied at a coating rate of 14 cc / m ^{2 with} a coating speed of 40 m / min, and was retained for 10 seconds under a steam far-infrared heater manufactured by Noritake Company Limited, heated to 110 ° C. Pure water was applied at 3 cc / m ² using a coater. The film temperature at this time was 40 degreeC. Next, washing with a fountain coater and draining with an air knife were repeated three times, and then the film was retained in a drying zone at 70 ° C. for 5 seconds for drying.
<Alkaline solution (S-1) composition>
Potassium hydroxide 8.55 parts by weight Water 23.235 parts by weight Isopropanol 54.20 parts by weight Surfactant (K-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂ OH) 1.0 part by weight Propylene glycol 13.0 parts by weight Antifoaming agent Surfinol DF110D (manufactured by Nissin Chemical Industry Co., Ltd.) 0.015 parts by weight The contact angle of the surface of the film after alkali treatment with water is 35 °, and the entire surface of the film is uneven. It was made hydrophilic evenly.

(Formation of alignment film (AL))
An aqueous solution of 50 parts by weight of glutaraldehyde was prepared, 0.05 part by weight of sodium sulfite was added to the aqueous solution, and left at room temperature for 4 hours. The solution was added to a water / methanol solution in which the following modified polyvinyl alcohol was dissolved to prepare an alignment film coating solution having the following composition.

<Composition of alignment film coating solution (ALL-1)>
The following modified polyvinyl alcohol 20 parts by weight Sodium sulfite (A-1) (n = 8.53) 0.05 part by weight Glutaraldehyde 0.5 part by weight Water 360 parts by weight Methanol 120 parts by weight

On the surface of the above-mentioned alkali-treated film, the alignment film coating solution was coated with a rod coater at a coating amount of 28 ml / m ² . The alignment film (AL-1) was produced by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 90 ° C. for 150 seconds.
In addition, pH value of the position of the center in the application width direction of the application surface after drying, and the position of both right and left ends was the range of 6.0-6.6.

  Next, the rubbing process was implemented in the longitudinal direction of the film.

(Formation of optically anisotropic layer)
A discotic liquid crystal coating liquid (DA-1) having the following composition is applied with a # 4 wire bar coater, heated in a high-temperature bath at 125 ° C. for 90 seconds to align the discotic liquid crystal, and then a high-pressure mercury lamp is used. Then, UV was irradiated at 500 mJ / cm ² and allowed to cool to room temperature to prepare an optical compensation sheet KS-1. The thickness of the optically anisotropic layer was 1.8 μm.

<Composition of discotic liquid crystal coating liquid (DA-1)>
The following discotic liquid crystal DLC-A 9.1 parts by weight Ethylene oxide-modified trimethylolpropane acrylate (V # 360, Osaka Organic Chemical Co., Ltd.) 0.9 parts by weight Irgacure 907 (Ciba Geigy) 3.0 parts by weight Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.1 parts by weight Methyl ethyl ketone 25.9 parts by weight Cellulose acetate butyrate (CAB551-0.2: manufactured by Eastman Chemical Co.) 0.2 parts by weight Orientation agent (Exemplary Compound (I -1)) 0.02 part by weight Inclination angle controlling agent (II-17) 0.02 part by weight Polymer (FP-1) containing the following fluoroaliphatic group 0.04 part by weight

When the tilt angle was measured using an ellipsometer (M-150, manufactured by JASCO Corporation), the discotic liquid crystal molecules were optically separated from the film surface by the angle (tilt angle) between the disc surface and the glass substrate plane. It increased from 3 degrees to 75 degrees toward the air interface (hybrid orientation), and it was found that the hybrid was oriented with an average tilt angle of about 40 degrees.
When the retardation of the optical compensation sheet KS-1 was measured by using an elipsometry (manufactured by JASCO Corporation, M-150), the in-plane retardation (Re) was 69 nm and the retardation Rth in the thickness direction was 108 nm. .
The optical compensation sheet KS-1 was sandwiched between crossed Nicol polarizing plates, and surface unevenness and poor alignment were confirmed. The evaluation of white spot unevenness and orientation was as follows, and the results are shown in Table 7.
(I) Planar unevenness The optical compensation sheet was inserted diagonally in a state under a polarizing plate crossed Nicol, and the number of planar unevenness having a size of several mm was counted.
(Ii) Alignment The optical compensation sheet was inserted into the extinction position under the condition of polarizing plate crossed Nicol, and the presence or absence of defects such as schlieren was confirmed.
(Iii) Evaluation of adhesion The optical compensation sheet KS-1 was attached to a glass plate using an acrylic adhesive and stored at 90 ° C. for 20 hours. The acrylic adhesive is the same as that used for assembling the liquid crystal display device, and the glass plate is the same as that used for the liquid crystal cell. The optical compensation sheet was peeled off from the glass plate in the vertical direction, and the adhesion was evaluated by examining the portion where the peeling residue occurred. Evaluation was performed in five stages from 0 (remarkably remaining peeling) to 5 (no remaining peeling was observed). The results are shown in Table 7.

(Tilt angle of the liquid crystal on the alignment layer side)
Table 2 below shows the correlation between the amount of A-1 added and the tilt angle of the liquid crystal on the alignment film side.

[Example 2]
(Preparation of transparent support)
The dope obtained in Example 1 was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, peeled off, and then dried with a cellulose acylate film CA-2 having a residual solvent amount of 0.3 wt% (thickness 60 μm). ) Was manufactured.
When the retardation of the produced cellulose acylate film CA-2 was measured, the retardation Rth in the thickness direction was 43 nm, and the in-plane retardation Re was 4 nm.

(Saponification treatment)
An alkaline solution (S-2) having the following contents kept at 25 ° C. was heated using an extrusion coater after colliding with 100 ° C. hot air on the cellulose acylate film (CA-2) and heating to 45 ° C. The coating was applied at a coating amount of 17 cc / m ² and a coating speed of 60 m / min. After 8 seconds, 5 cc / m ^{2 of} pure water was applied again using an extrusion coater. The film temperature at this time was 45 ° C. Next, 1000 cc / m ² of pure water was applied using an extrusion type coater, washed with water, and after 5 seconds, 100 m / s of wind was collided with the water application surface from an air knife. The washing with the extrusion coater and the draining with the air knife were repeated twice, and then the film was retained in the drying zone at 80 ° C. for 10 seconds and dried.
<Alkaline solution (S-2) composition>
Sodium hydroxide 6.5 parts by weight Water 55.49 parts by weight n-propanol 37.0 parts by weight Surfactant (K-2: ethylenediamine ethylene oxide adduct)
1.0 part by weight Antifoaming agent Surfinol 104 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.01 part by weight

(Formation of alignment film (AL))
An alignment film material, a curing compound, and a nucleophile were separately added to a water / methanol mixed solution to prepare an alignment film coating solution having the following composition.
On the saponified cellulose acylate film CA-2 produced, an alignment film coating solution (ALL-2) was applied with a rod coater at a coating amount of 28 ml / m ² . Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
The pH values at the center and the left and right ends in the coating width direction of the coated surface after drying were in the range of 5.0 to 6.05.

<Composition of alignment film coating solution (ALL-2)>
The following modified polyvinyl alcohol 13.5 parts by weight Polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) 1.5 parts by weight Potassium thiocyanate (A-2) (n = 6.70) 0.05 parts by weight Water 361 parts by weight Methanol 119 parts by weight Succinaldehyde 0.5 parts by weight

  Next, the modified polyvinyl alcohol film was rubbed so as to be oriented in a direction parallel to the longitudinal direction of the cellulose acylate film CA-2.

(Formation of optically anisotropic layer)
Using the discotic liquid crystal coating liquid DA-1 used in Example 1, an optical compensation sheet KS-2 having an optically anisotropic layer thickness of 1.8 μm was prepared in the same manner as in Example 1.

When the tilt angle was measured using an ellipsometer (M-150, manufactured by JASCO Corporation), the discotic liquid crystal molecules had an optical angle from the film surface. It increased from 3 degrees to 75 degrees toward the air interface (hybrid orientation), and it was found that the hybrid was oriented with an average tilt angle of about 40 degrees.
When the retardation of the optical compensation sheet KS-2 was measured along the rubbing direction of the alignment film, the in-plane retardation (Re) was 65 nm and the retardation Rth in the thickness direction was 112 nm. The optical compensation sheet KS-2 was sandwiched between crossed Nicol polarizing plates, and surface unevenness and poor alignment were confirmed.
Further, adhesion evaluation was performed in the same manner as in Example 1 with the optical compensation sheet KS-2.
The results are shown in Table 7.

(Tilt angle of the liquid crystal on the alignment layer side)
Table 3 below shows the correlation between the added amount of A-2 and the tilt angle of the liquid crystal on the alignment film side.

[Example 3]
(Preparation of transparent support)
The dope obtained in Example 1 was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, peeled off, and then dried with a cellulose acylate film CA-3 having a residual solvent amount of 0.3% by weight (thickness 40 μm). ) Was manufactured.
When the retardation of the produced cellulose acylate film CA-3 was measured, the retardation Rth in the thickness direction was 32 nm, and the in-plane retardation Re was 3 nm.

(Saponification and alignment film formation)
The cellulose acylate film (CA-3) was saponified in the same manner as in Example 1 except that the alkaline solution (S-3) having the following contents was used.
<Alkaline solution (S-3) composition>
Potassium hydroxide 4.0 parts by weight Water 42.7 parts by weight Methyl cellosolve 40.0 parts by weight Tetraethylene glycol 12.0 parts by weight Surfactant [K-3: C ₉ H ₁₉ Ph (OCH ₂ CH ₂ ) ₃ SO ₃ Na (Ph is a phenylene group)]
1.3 parts by weight Antifoaming agent Pluronic TR70 (Asahi Denka Kogyo Co., Ltd.) 0.1 parts by weight

Thereafter, the coating film was applied and dried in the same manner as the alignment film of Example 1 except that the alignment film coating solution (ALL-3) having the following composition was used, and then the rubbing treatment was performed to form the alignment film (AL-3). Formed.
<Composition of alignment film coating solution (ALL-3)>
The following modified polyvinyl alcohol 20 parts by weight Sodium thiosulfate (A-3) (n = 8.95) 0.01 part by weight Water 360 parts by weight Methanol 120 parts by weight Adipaldehyde 0.5 part by weight

(Formation of optically anisotropic layer)
A discotic liquid crystal coating solution (DA-2) having the following composition was applied with a # 4 wire bar coater, heated in a high-temperature bath at 125 ° C. for 150 seconds to align the discotic liquid crystal, and then used a high-pressure mercury lamp. Then, UV was irradiated at 500 mJ / cm ² and allowed to cool to room temperature to prepare an optical compensation sheet KS-4.
<Composition of discotic liquid crystal coating liquid (DA-2)>
Discotic liquid crystal DLC-A 9.1 parts by weight Ethylene oxide modified trimethylolpropane acrylate (V # 360, Osaka Organic Chemical Co., Ltd.) 0.9 parts by weight Cellulose acetate butyrate (CAB551-0.2 Eastman Chemical) 0 0.2 part by weight Cellulose acetate butyrate (CAB531-1 Eastman Chemical) 0.05 part by weight Irgacure 907 3.0 part by weight Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.1 part by weight Methyl ethyl ketone 25.9 Parts by weight

The thickness of the optically anisotropic layer was 1.8 μm. When the retardation of the optical compensation sheet KS-4 was measured along the rubbing direction of the alignment film, the in-plane retardation (Re) was 33 nm, and the retardation Rth in the thickness direction was 120 nm. The optical compensation sheet KS-3 was sandwiched between crossed Nicol polarizing plates, and surface unevenness and poor alignment were confirmed.
Further, adhesion evaluation was performed in the same manner as in Example 1 with the optical compensation sheet KS-3.
The results are shown in Table 7.

(Tilt angle of the liquid crystal on the alignment layer side)
Table 4 below shows the correlation between the added amount of A-3 and the tilt angle of the liquid crystal on the alignment film side.

[Example 4]
(Saponification and alignment film formation)
A cellulose acetate film (CA-1) is passed through a dielectric heating roll having a temperature of 60 ° C. and heated to a film surface temperature of 30 ° C., and then an alkali solution (S-4) having the following composition is used with a rod coater. After being transported so as to stay for 20 seconds under a steam far infrared heater manufactured by Noritake Co., Ltd., which was applied at a coating amount of 10 cc / m ² and heated to 110 ° C., it was purified using a rod coater. Water was applied at 3 cc / m ² . The film temperature at this time was 40 degreeC. Next, washing with a fountain coater and draining with an air knife were repeated three times, and then the film was retained in a drying zone at 70 ° C. for 5 seconds for drying.
<Alkaline treatment liquid (S-4) composition>
Potassium hydroxide 5.7 parts by weight Water 33.3 parts by weight n-Propyl alcohol 49.8 parts by weight Ethylene glycol 10.0 parts by weight Antifoaming agent Pluronic TR70 (Asahi Denka Kogyo Co., Ltd.) 0.01 parts by weight

Thereafter, the coating film was applied and dried in the same manner as the alignment film of Example 1 except that the alignment film coating solution having the following composition was used, and then a rubbing treatment was performed.
<Composition of alignment film coating solution (ALL-4)>
The following modified polyvinyl alcohol 20 parts by weight Thiourea (A-4) (n = 7.27) 0.01 part by weight Water 360 parts by weight Methanol 120 parts by weight Sebacinaldehyde 0.5 part by weight

(Preparation of optical compensation sheet (KS-4))
On the support after applying the alignment film of Example 4, an optically anisotropic layer having the following contents was coated to prepare an optical compensation sheet (KS-4).
Optically anisotropic layer: 38.1 parts by weight of the following rod-like liquid crystal compound (LC), 1.14 parts by weight of the photopolymerization initiator “Irgacure 907”, 0.38 parts by weight of the sensitizer “Kayakya DETX”, the following orientation A mixture (DA-3) of 0.19 parts by weight of a modifier, 0.04 parts by weight of glutaraldehyde, and 60.15 parts by weight of methyl ethyl ketone was applied with a wire bar, and heated with hot air at 125 ° C. and 1 m / second for 3 minutes. . Next, it was irradiated with light for 30 seconds using a 120 W / cm high-pressure mercury lamp at 100 ° C. and allowed to cool to room temperature. The film thickness of the optically anisotropic layer was 0.8 μm.

光学的異方性層の厚さは、１．８μｍであった。光学補償シートＫＳ−４をクロスニコル偏光板間に挟み、面状ムラ、配向不良の確認を行った。
また、光学補償シートＫＳ−４で、実施例１と同様に密着評価を実施した。
それらの結果を表７に示す。

The thickness of the optically anisotropic layer was 1.8 μm. The optical compensation sheet KS-4 was sandwiched between crossed Nicol polarizing plates, and surface unevenness and poor alignment were confirmed.
Further, adhesion evaluation was performed in the same manner as in Example 1 with the optical compensation sheet KS-4.
The results are shown in Table 7.

(Tilt angle of the liquid crystal on the alignment layer side)
Table 5 below shows the correlation between the added amount of A-4 and the tilt angle of the liquid crystal on the alignment film side.

[Comparative Example 1]
The alignment layer (ALR-1) was formed using a composition obtained by removing the nucleophilic agent (A-1) from the alignment layer composition of Example 1 instead of the alignment layer composition of Example 1. Produced an optical compensation sheet (KSR-1) in the same manner as in Example 1.
The optical compensation sheet KSR-1 was sandwiched between crossed Nicol polarizing plates, and surface unevenness was confirmed.
Further, adhesion evaluation was performed in the same manner as in Example 1 with the optical compensation sheet KSR-1.
The results are shown in Table 7.

[Comparative Example 2]
Instead of the composition for alignment layer in Example 1, CH ₃ COOH (n = 4.3) was used in place of the nucleophile (A-1) of the composition for alignment layer in Example 1, and the alignment layer ( An optical compensation sheet (KSR-2) was prepared in the same manner as in Example 1 except that ALR-2) was formed.
The optical compensation sheet KSR-2 was sandwiched between crossed Nicol polarizing plates, and surface unevenness was confirmed.
Further, adhesion evaluation was performed in the same manner as in Example 1 with the optical compensation sheet KSR-2.
The results are shown in Table 7.

(Tilt angle of the liquid crystal on the alignment layer side)
Table 6 below shows the correlation between the amount of the additive added and the tilt angle of the liquid crystal on the alignment film side.

From the results shown in Table 7, the optical compensation sheets (KS-1) to (KS-4) of the present invention showed excellent planarity (no white spots and good orientation) and excellent adhesion. . On the other hand, in the comparative examples (KSR-1) and (KSR-2), the planar shape of the alignment film was lowered.
As described above, the optical compensation sheet of the present invention showed good performance.

[Example 5]
(Preparation of transparent support)
The following cellulose acetate solution composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

(Cellulose acetate solution composition)
Cellulose acetate with 6-position substitution degree 0.90 (Linter) 80 parts by weight Cellulose acetate with 6-position substitution degree 0.90 (Linter) 20 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) 54 parts by weight 1-butanol (third solvent) 11 parts by weight

In a separate mixing tank, 4 parts by weight of cellulose acetate (linter) having a substitution degree of 6-position of 0.90, 16 parts by weight of the retardation increasing agent described in Example 1, silica fine particles “AEROSIL R812” (trade name; Nippon Aerosil ( 0.5 parts by weight, 87 parts by weight of methylene chloride and 13 parts by weight of methanol were added and stirred while heating to prepare a retardation increasing agent solution.
A dope was prepared by mixing 464 parts by weight of the cellulose acetate solution with 36 parts by weight of the retardation increasing agent solution and stirring sufficiently. The addition amount of the retardation increasing agent was 5.0 parts by weight with respect to 100 parts by weight of cellulose acetate.

The obtained dope was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, peeled off the film having a residual solvent amount of 43% by weight, and then dried in a width direction using a tenter with a drying air of 140 ° C. % Stretched. Then, it dried with 135 degreeC drying air for 20 minutes, and manufactured the cellulose acetate film (CA-4) whose residual solvent amount is 0.3 weight%.
The width of the obtained cellulose acetate film (CA-4) was 1340 mm, and the thickness was 82 μm. It was 41 nm when the retardation value (Re) in wavelength 590nm was measured using the ellipsometer (M-150, JASCO Corporation make). Moreover, it was 173 nm when the retardation value (Rth) in wavelength 590nm was measured.

(Saponification treatment and formation of alignment film (AL))
The produced cellulose acetate film (CA-4) was treated in the same manner as the alkali saponification treatment of Example 1. The surface energy of the cellulose acetate film (CA-4) was determined by a contact angle method and found to be 62 mN / m.
On this cellulose acetate film (CA-4), an alignment film coating solution (ALL-5) having the following composition was coated at a coating amount of 26 ml / m ² with a rod coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.

<Alignment film coating solution (ALL-5)>
Polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) 10 parts by weight The following modified polyvinyl alcohol 10 parts by weight Potassium hydroxide (A-5) (n = 6.58) 0.008 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde (crosslinking agent) 0.5 parts by weight

  The alignment film was rubbed in the direction of 45 ° with the slow axis (measured at a wavelength of 632.8 nm) of the cellulose acetate film (CA-4).

(Formation of optically anisotropic layer)
41.01 parts by weight of the above discotic liquid crystalline compound (DLC-A), ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4.06 parts by weight, cellulose acetate butyrate ( CAB531-1, manufactured by Eastman Chemical Co., Ltd.) 0.35 parts by weight, photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 1.35 parts by weight, sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0 .45 parts by weight, 0.45 part by weight of a fluorosurfactant (Megafac F780F manufactured by Dainippon Ink Co., Ltd.) was dissolved in 102 parts by weight of methyl ethyl ketone, and this coating solution was applied to the alignment film on # 3.6. The wire bar was continuously applied and heated at 130 ° C. for 2 minutes to align the discotic liquid crystalline compound. Next, UV irradiation was performed for 1 minute using a 120 W / cm high-pressure mercury lamp at 100 ° C. to polymerize the discotic liquid crystalline compound. Then, it stood to cool to room temperature. In this manner, an optical compensation sheet (KS-5) with an optical anisotropic layer was produced.
The Re retardation value of the optically anisotropic layer measured at a wavelength of 546 nm was 38 nm. The angle (tilt angle) between the disk surface and the first transparent support surface was 34 ° on average.

(Tilt angle of the liquid crystal on the alignment layer side)
The correlation between the added amount of A-5 and the tilt angle of the liquid crystal on the alignment film side is shown below.

When the polarizing plate was arranged in a crossed Nicol arrangement and the unevenness of the obtained optical compensation sheet was observed, the unevenness could not be detected even when viewed from the front and the direction inclined to 60 ° from the normal line.
(Preparation of protective film with antireflection film (AF))
On the above cellulose acylate film (CA-4), “Pernox C-4456-S7” [ATO-dispersed hard coat agent (solid content 45 wt%): manufactured by Nippon Pernox Co., Ltd.] was applied and dried. The film was cured by irradiating with ultraviolet rays to form a 1 μm thick conductive layer (ECL). The film had a surface resistance of the order of 10 ⁸ Ω / □.
The surface resistivity was measured using a resistivity meter “MCP-HT260” manufactured by Mitsubishi Chemical Corporation under the same condition after leaving the sample to stand under the condition of (25 ° C./65% RH) for 1 hour.
An antireflection film as described below was produced on this film.

{Anti-glare hard coat layer coating solution (HCL-1)}
50 parts by weight of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Explosives Co., Ltd.], 2 parts by weight of a curing initiator “Irgacure 184” (manufactured by Ciba Geigy), as the first light-transmitting fine particles 2. Acrylic-styrene beads [manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index 1.55] 5 parts by weight, styrene beads [manufactured by Soken Chemical Co., Ltd., particle size 3. 5 μm, refractive index 1.60] 5.2 parts by weight, silane coupling agent “KBM-5103” [manufactured by Shin-Etsu Chemical Co., Ltd.] 10 parts by weight, and the following fluoropolymer (PF-2) 0.03 A cellulose acylate fill with the above conductive layer (ECL) unrolled from a roll form was prepared by mixing 50 parts by weight of toluene with 50 parts by weight of toluene. A dry film thickness of 6.0 μm was applied onto the film, and after drying the solvent, using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), an illuminance of 400 mW / cm ² and an irradiation amount The coating layer was cured by irradiating 300 mJ / cm ² of ultraviolet rays to prepare an antiglare hard coat layer (refractive index 1.52) (HC-3).

{Formation of low refractive index layer (LL-1)}
On the antiglare layer, a coating solution for low refractive index layer (LLL-1) described later was applied using a micro gravure coater. After drying at 80 ° C. and using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less, the illuminance is 550 mW / A low refractive index layer (LL-1) (refractive index of 1.43, film thickness of 86 nm) was formed by irradiating ultraviolet rays with a cm ² and an irradiation amount of 600 mJ / cm ² . Thus, the protective film (AF-1) for polarizing films with the antireflection film of this invention was produced.
The obtained antireflection film had an average reflectance of 2.1% and a haze of 43%.

(Preparation of polarizing film (HF))
PVA having an average polymerization degree of 4000 and a saponification degree of 99.8 mol% was dissolved in water to obtain a 4.0% aqueous solution. This solution was band-cast using a die having a taper and dried to form a film so that the width before stretching was 110 mm, the thickness was 120 μm at the left end, and 135 μm at the right end.
The film was peeled off from the band, and obliquely stretched in the 45 ° direction in a dry state, and immersed in an aqueous solution of 0.5 g / L iodine and 50 g / L potassium iodide for 1 minute at 30 ° C., and then 100 g boric acid. / L, potassium iodide 60 g / L in an aqueous solution at 70 ° C. for 5 minutes, further washed with water at 20 ° C. for 10 seconds and then dried at 80 ° C. for 5 minutes to obtain an iodine-based polarizing film (HF-1 ) The polarizing film had a width of 660 mm and a thickness of 20 μm on both sides.

(Preparation of viewing side polarizing plate (SHB))
The film surface opposite to the optically anisotropic layer of the optical compensation sheet (KS-5) with an optically anisotropic layer was treated in the same manner as the alkali saponification treatment of Example 1, and the above antireflection film Polarized light produced using a polyvinyl alcohol-based adhesive on each of the film surfaces of the protective film (AF-1) that was saponified on the side opposite to the antireflection film in the same manner as the alkali saponification treatment of Example 1. A film (HF-1) was attached.
The transmission axis of the polarizing film and the slow axis of the cellulose acetate film (CA-5) were arranged in parallel. The transmission axis of the polarizing film and the slow axis of the triacetyl cellulose film were arranged so as to be orthogonal to each other. In this way, a polarizing plate (SHB-1) was produced.

(Preparation of back side polarizing plate (BHB))
The film surface obtained by treating the film surface opposite to the optically anisotropic layer of the optical compensation sheet with an optically anisotropic layer (KS-5) in the same manner as the alkali saponification treatment of Example 1, and the above cellulose acylate film Each of the film surfaces obtained by saponifying one side of (CA-4) in the same manner as the alkali saponification treatment of Example 1 was attached using a polyvinyl alcohol-based adhesive. .
The transmission axis of the polarizing film and the slow axis of the cellulose acetate film (CA-4) were arranged in parallel. The transmission axis of the polarizing film and the slow axis of the cellulose acylate film were arranged so as to be orthogonal to each other. Thus, the back side polarizing plate (BHB-1) was produced.

[Example 6]
(Preparation of transparent support)
Into the mixing tank, 16 parts by weight of the retardation increasing agent used in Example 5, 80 parts by weight of methylene chloride and 20 parts by weight of methanol were added and stirred while heating to prepare a retardation increasing agent solution.
25 parts by weight of the retardation increasing agent solution was mixed with 474 parts by weight of the cellulose acetate solution prepared in Example 5, and the dope was prepared by sufficiently stirring. The addition amount of the retardation increasing agent was 3.5 parts by weight with respect to 100 parts by weight of cellulose acetate.

The obtained dope was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried for 1 minute, peeled off, and then dried with a 140 ° C. dry cellulose acylate film (CA-5 having a residual solvent amount of 0.3% by weight). ) Was manufactured.
The obtained cellulose acylate film (CA-5) had a width of 1500 mm and a thickness of 65 μm. It was 4 nm when the retardation value (Re) in wavelength 590nm was measured using the ellipsometer (M-150, JASCO Corporation make). Moreover, it was 78 nm when the retardation value (Rth) in wavelength 590nm was measured.

(Saponification treatment)
The cellulose acylate film (CA-5) was saponified in the same manner as the alkali saponification method of Example 2. The surface energy of the saponified surface of cellulose acylate (CA-5) was determined by a contact angle method and found to be 63 mN / m.

(Formation of alignment film)
On the saponified surface of the produced cellulose acylate film (CA-5), a coating solution having the following composition was applied at an application amount of 28 ml / m ² with an extrusion coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.

<Alignment film coating solution composition (ALL-6)>
Modified polyvinyl alcohol of Example 5 10 parts by weight Potassium sulfite (A-6) (n = 8.53) 0.008 part by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 part by weight

Next, the modified polyvinyl alcohol film was rubbed so as to be oriented in a direction parallel to the longitudinal direction of cellulose acylate (CA-5).
(Formation of alignment film)
The alignment film coating solution (ALL-6) was applied at a coating amount of 35 ml / m ² using the following die coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
When the pH of the coated surface after drying was measured, the value was 6.1. Moreover, the pH value of the position of the center in the application | coating width direction and both right-and-left both ends was the range of 5.00-6.20.
(Die coater configuration)
The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and a length of the slot 16 of 50 mm. I used one. The gap between the upstream lip land 18a and the web 12 is 50 μm longer than the gap between the downstream lip land 18b and the web 12 (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web 12 is set. _GL was set to 50 μm. Further, the gap G _B between the gap G _S, and the back plate 40a and the web 12 between the side plate 40b and the web 12 of the decompression chamber 40 were both 200 [mu] m.

(Formation of optically anisotropic layer)
On the alignment film, 41.01 parts by weight of a discotic liquid crystalline compound (DLC-A), 4.06 parts by weight of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate 0.90 parts by weight of butyrate (CAB551-0.2, manufactured by Eastman Chemical), 0.23 parts by weight of cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical), photopolymerization initiator (Irgacure 907) 1.35 parts by weight, sensitizer (Kayacure DETX) 0.45 parts by weight, fluorine surfactant (F-2) 0.40 part by weight of the following structure dissolved in methyl ethyl ketone 102 parts by weight and coating solution This was applied with a wire bar # 3.4. This was heated in a constant temperature zone of 130 ° C. for 2 minutes to align the discotic liquid crystalline compound. Next, UV irradiation was performed for 1 minute using a 120 W / cm high-pressure mercury lamp in an atmosphere of 60 ° C. to polymerize the discotic liquid crystalline compound. Then, it stood to cool to room temperature. In this way, an optically anisotropic layer having a film thickness of 1.8 μm was formed to produce an optical compensation sheet (KS-6).

The Re retardation value of the optically anisotropic layer measured at a wavelength of 546 nm was 40 nm. The angle (tilt angle) between the disk surface and the first transparent support surface was 37 ° on average.
When the polarizing plate was arranged in a crossed Nicol arrangement and the unevenness of the obtained optical compensation sheet was observed, the unevenness could not be detected even when viewed from the front and the direction inclined to 60 ° from the normal line.

(Preparation of protective film with antireflection film)
[Preparation of antireflection film (AF)]
[Preparation of coating liquid for hard coat layer (HCL-1)]
750.0 parts by weight of trimethylolpropane triacrylate [“TMPTA” manufactured by Nippon Kayaku Co., Ltd.], 270.0 parts by weight of poly (glycidyl methacrylate) having a weight average molecular weight of 3000, 730.0 parts by weight of methyl ethyl ketone, 500. 0 parts by weight and 50.0 parts by weight of a photopolymerization initiator “Irgacure 184” [manufactured by Ciba Specialty Chemicals Co., Ltd.] were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

{Production of titanium dioxide fine particles (T-1)}
Cobalt-containing titanium dioxide fine particles (T-1) in which cobalt is doped into titanium dioxide particles in the same manner as in this publication except that iron (Fe) is changed to cobalt based on JP-A-5-330825. Was made. The doped amount of cobalt was 98.5 / 1.5 in terms of Ti / Co (weight ratio). The produced titanium dioxide fine particles had a rutile-type crystal structure, the average primary particle size was 40 nm, and the specific surface area was 44 m ² / g.

{Preparation of Titanium Dioxide Fine Particle Dispersion (TL-1)}
100 g of the titanium dioxide fine particles (T-1), 20 g of a polymer dispersant (DP-1) having the following structure, and 360 g of cyclohexanone were added and dispersed together with zirconia beads having a particle diameter of 0.1 mm by dynomill. The dispersion temperature was 35 to 40 ° C. for 5 hours. A titanium dioxide fine particle dispersion (TL-1) having an average diameter of 55 nm with a particle diameter of 300 nm or more being 0% was prepared.

[Preparation of Medium Refractive Index Layer Coating Solution (MLL-1)]
88.9 parts by weight of the above-mentioned titanium dioxide fine particle dispersion (TL-1), 58.4 parts by weight of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“DPHA”), a photopolymerization initiator “Irgacure 907” [Ciba Specialty Chemicals Co., Ltd.] 3.1 parts by weight, photosensitizer “Kayacure DETX” [Nippon Kayaku Co., Ltd.] 1.1 parts by weight, methyl ethyl ketone 482.4 parts by weight, and cyclohexanone 1869.8 parts by weight were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a medium refractive index layer coating solution (MLL-1).

[Preparation of coating solution for high refractive index layer (HLL-1)]
In addition to 586.8 parts by weight of the above titanium dioxide dispersion (TL-1), 47.9 parts by weight of “DPHA”, 4.0 parts by weight of “Irgacure 907”, 1.3 parts by weight of “Kayacure DETX”, 455. 8 parts by weight and 1427.8 parts by weight of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for high refractive index layer (HLL-1).

[Preparation of coating solution for low refractive index layer (LLL-1)]
"DPHA" 1.4 parts by weight, fluorine polymer (PF-1) 5.6 parts by weight, hollow silica (average particle size 40 nm, shell layer thickness 7 nm, refractive index 1.31, isopropanol 18% by weight) 20.0 parts by weight, 0.7 parts by weight of reactive silicone “RMS-033” (manufactured by Gelest), 6.2 parts by weight of sol solution a having the following contents, and 0.2 parts by weight of “Irgacure 907” were added to methyl ethyl ketone 315 The mixture was added to 9 parts by weight and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for low refractive index layer (LLL-1).

[Preparation of Sol Solution a]
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane “KBM5103” [manufactured by Shin-Etsu Chemical Co., Ltd.], 3 parts of diisopropoxyaluminum ethyl acetoacetate are added and mixed. Further, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution a. The weight average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. From the gas chromatographic analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

[Preparation of antireflection film (AF-1)]
On the cellulose acylate film (CA-1) in the roll form, the hard coat layer coating solution (HCL-1) was applied using a reverse gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp [manufactured by Eye Graphics Co., Ltd.] of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^2. Irradiation with an irradiation amount of 300 mJ / cm ² was applied to cure the coating layer to form a hard coat layer (HC-1) having a thickness of 8 μm. On the obtained hard coat layer, a coating solution for medium refractive index layer (MLL-1), a coating solution for high refractive index layer (HLL-1), and a coating solution for low refractive index layer (LLL-1), Coating was performed continuously using a reverse gravure coater having three coating stations.

The medium refractive index layer was dried at 100 ° C. for 2 minutes, and the ultraviolet curing condition was an air-cooled metal halide lamp [I Graphics, which was purged with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. Made by Co., Ltd.], and the irradiation amount was 400 mW / cm ² and the irradiation amount was 400 mJ / cm ² . The medium refractive index layer (ML-1) after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying conditions for the high refractive index layer were 90 ° C., 1 minute, 100 ° C., 1 minute, and the ultraviolet curing conditions were carried out with nitrogen purge so that the atmosphere had an oxygen concentration of 1.0% by volume or less. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm, the irradiation dose was 600 mW / cm ² and the irradiation dose was 600 mJ / cm ² . The cured high refractive index layer (HL-1) had a refractive index of 1.905 and a film thickness of 107 nm.

The low refractive index layer was dried at 120 ° C. for 150 seconds, further dried at 140 ° C. for 8 minutes, and then a 240 W / cm air-cooled metal halide lamp [manufactured by Eye Graphics Co., Ltd.] under a nitrogen purge. Using, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² were irradiated. The low refractive index layer (LL-1) after curing had a refractive index of 1.43 and a film thickness of 100 nm.
As described above, a cellulose acylate film (AF-2) with an antireflection film was produced.

(Preparation of viewing side polarizing plate (SHB))
The film surface on the opposite side of the optically anisotropic layer with the optically anisotropic layer (KS-6) treated in the same manner as the alkali saponification treatment of Example 1, and the above antireflection film Polarized light produced using a polyvinyl alcohol-based adhesive on each of the film surfaces of the protective film (AF-2) that had been saponified on the side opposite to the antireflection film in the same manner as the alkali saponification treatment of Example 1. A film (HF-1) was attached.
The transmission axis of the polarizing film and the slow axis of the cellulose acetate film (CA-5) were arranged in parallel. The transmission axis of the polarizing film and the slow axis of the triacetyl cellulose film were arranged so as to be orthogonal to each other. In this way, a polarizing plate (SHB-2) was produced.

(Preparation of back side polarizing plate (BHB))
An optical compensation sheet (KS-6) was attached to one side of the polarizing film (HF-1) using a polyvinyl alcohol-based adhesive. In addition, a single-side saponification treatment was performed on an 80 μm-thick triacetyl cellulose film (TD-80U: manufactured by Fuji Photo Film Co., Ltd.) in the same manner as the alkali saponification treatment of Example 1, and a polyvinyl alcohol adhesive was used. Pasted on the opposite side of the polarizing film.
The transmission axis of the polarizing film and the slow axis of the cellulose acetate film (CA-5) were arranged in parallel. The transmission axis of the polarizing film and the slow axis of the triacetyl cellulose film were arranged so as to be orthogonal to each other. Thus, a back side polarizing plate (BHB-2) was produced.

(Preparation 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 6 μm. A bend-aligned liquid crystal cell was prepared by injecting a liquid crystal compound (ZLI1132, manufactured by Merck & Co., Inc.) having a Δn (difference between the refractive indexes ne and no) of 0.1396. The size of the liquid crystal cell was 20 inches.
The viewing side polarizing plate (SHB-1) prepared in Example 5 is pasted on the air side and the back side polarizing plate (BHB-1) is pasted on the back side so as to sandwich the prepared bend alignment cell. I attached. 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.
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. Using the measurement ratio (EZ-Contrast160D, manufactured by ELDIM) as the contrast ratio of the transmittance ratio (white display / black display), the viewing angle can be adjusted in eight steps from black display (L1) to white display (L8). It was measured.
As an evaluation measure of the viewing angle, the contrast ratio of the field image is maintained at 10 or more, and the gradation inversion on the black side does not occur (that is, the inversion occurs between the black display (L1) and the next level (L2)). None) A range of open angle values was used. Table 9 shows the measurement results.

(Tilt angle and viewing angle of the liquid crystal on the alignment layer side)
Further, the correlation between the addition amount of A-6 and the tilt angle and viewing angle of the liquid crystal on the alignment film side is shown below.

(Evaluation of unevenness on LCD panel)
The display panel of the liquid crystal display device of Example 5 was adjusted to a halftone on the entire surface, and unevenness was evaluated. In Example 5, no unevenness was observed from any direction.

(Evaluation with TN liquid crystal cell)
A pair of polarizing plates provided in a liquid crystal display device (AQUAS LC20C1S, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and the polarizing plate (HB-2) prepared in Example 6 is optically replaced. The compensation sheets (KS-6) were attached to the viewer side and the backlight side one by one through an adhesive so that the compensation sheet (KS-6) was on the liquid crystal cell side. The transmission axis of the polarizing plate on the viewer side and the transmission axis of the polarizing plate on the backlight side were arranged to be in the O mode.
About the produced liquid crystal display device, the viewing angle was measured in eight steps from black display (L1) to white display (L8) using the measuring machine (EZ-Contrast160D, ELDIM company make). Table 11 shows the measurement results.

(Tilt angle and viewing angle of the liquid crystal on the alignment layer side)
Further, the correlation between the addition amount of A-6 and the tilt angle and viewing angle of the liquid crystal on the alignment film side is shown below.

(Evaluation of unevenness on LCD panel)
The display panel of the liquid crystal display device of Example 6 was adjusted to a halftone on the entire surface, and unevenness was evaluated. In Example 6, no unevenness was observed when viewed from any direction.

(Evaluation with VA liquid crystal cell)
A polarizing plate (HB-1) produced in Example 5 of the present invention instead of the polarizing plate on the viewing side provided in the 22-inch liquid crystal display device: TH22-LH10 type (manufactured by Matsushita Electric Co., Ltd.) in the VA mode ) Optical compensation sheet (KS-5) was attached to the viewer side through an acrylic adhesive so that it would be on the liquid crystal cell side. When the display panel of this liquid crystal display device was adjusted to a halftone on the entire surface and unevenness was evaluated, unevenness was not observed from any direction.
Moreover, the polarizing plate (HB) produced in Example 5 of this invention instead of the protective film of the visual recognition side provided in 20-inch liquid crystal display device: W20-1c3000 type (made by Hitachi, Ltd.) in IPS mode. A piece of optical compensation sheet (KS-5) of -1) was attached to the viewing side via an acrylic pressure-sensitive adhesive so as to be on the liquid crystal cell side. When the display panel of this liquid crystal display device was adjusted to a halftone on the entire surface and unevenness was evaluated, unevenness was not observed from any direction.

[Examples 7 to 10]
In Example 1, in place of the nucleophile (A-1) of the optically anisotropic layer, the same molar amount of the nucleophile (A-7) shown in Table 13 below was used, respectively, and the crosslinking agent instead of the crosslinking agent glutaraldehyde. An optical compensation sheet was prepared in the same manner as in Example 1 except that the same mole of (A-8) was used. Using the optical compensation sheet, a polarizing plate (Example 7) was prepared in the same manner as in Example 5. Also in Examples 2 to 4, an optical compensation sheet was prepared using the nucleophile (A-7) and the crosslinking agent (A-8) in the same manner as described above, and each polarizing plate (Examples 8 to 10) was prepared in the same manner as described above. )created.

  As a result of evaluating each obtained polarizing plate similarly to Example 5, all the polarizing plates showed the same favorable performance as the polarizing plate of Example 5. FIG.

It is the cross-sectional schematic diagram which showed the outline of the slot die coating in the optical compensation sheet | seat of this invention. FIG. 6 is two cross-sectional views comparing the cross-sectional shape of a slot die that can be used for manufacturing the optical compensation sheet of the present invention and the cross-sectional shape of a conventional slot die. It is a perspective view which shows the slot die which can be used for optical compensation sheet manufacture of this invention, and its periphery. It is an expanded sectional view which shows the decompression chamber and web which can be used for optical compensation sheet manufacture of this invention. It is an expanded sectional view which shows the decompression chamber and web which can be used for optical compensation sheet manufacture of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Coater 11 Backup roll 12 Web 13 Slot die 14 Coating liquid 14a Bead 14b Coating film 15 Pocket 16 Slot 16a Opening part 17 Tip lip 18 Flat part 18a Upstream lip land 18b Downstream lip land 30 Slot die 31a Upstream lip land 31b Downstream lip land 32 Pocket 33 Slot 40 Decompression chamber 40a Back plate 40b Side plate I _LO Land length of downstream lip land I _UP Land length of upstream lip land LO Downstream lip land and upstream lip land web Distance difference (over byte length)
G _L Tip gap between the lip and the web (when the slot die has an overbite shape, it indicates the gap between the downstream lip land and the web)
G _B Gap between back plate and web G _S Gap between side plate and web

Claims (17)

An optical compensation sheet in which an alignment film and an optically anisotropic layer obtained by aligning and polymerizing a liquid crystalline compound are laminated in this order on a transparent support that has been subjected to adhesion imparting treatment in advance,
The alignment film comprises a layer obtained by heat-curing a composition for forming an alignment film containing at least one aldehyde compound having two or more aldehyde groups and at least one nucleophilic agent having a nucleophilic constant (n) of 5 or more and 10 or less. An optical compensation sheet characterized by the above.   The optical compensation sheet according to claim 1, wherein the nucleophilic agent has a nucleophilic constant (n) of 6.5 or more and 10 or less.   3. The optical compensation sheet according to claim 1, wherein the nucleophile is a sulfite that generates sulfite ions or a thiosulfate that generates thiosulfate ions.   4. The alignment film according to claim 1, wherein the alignment film is a cured film formed by applying and drying an alignment film forming composition containing polyvinyl alcohol and / or modified polyvinyl alcohol as a main component. The optical compensation sheet according to one.   The optical compensation sheet according to any one of claims 1 to 4, wherein the optically anisotropic layer contains a fluorine-containing surfactant.   The optical compensation sheet according to any one of claims 1 to 5, wherein the optically anisotropic layer contains a polymer containing a fluoroaliphatic group.   The adhesion imparting treatment applied to the transparent support is an alkali saponification treatment comprising applying a saponification treatment by applying an alkaline solution containing at least a water-soluble organic solvent and a surfactant and / or a compatibilizing agent. The optical compensation sheet according to any one of claims 1 to 6.   8. The transparent support according to claim 1, wherein the Re retardation value is in the range of 0 to 200 nm and the Rth retardation value is in the range of 0 to 400 nm. Optical compensation sheet. The above-mentioned transparent support is a cellulose acylate film, and the cellulose acylate film is a cellulose acylate in a range satisfying the following formulas (1) and (2) simultaneously. The optical compensation sheet according to any one of 8.
Formula (1): 2.3 ≦ SA ′ + SB ′ ≦ 3.0
Formula (2): 0 ≦ SA ′ ≦ 3.0
(In the formula, SA ′ is the substitution degree of the acetyl group substituting the hydrogen atom of the hydroxyl group of cellulose, and SB ′ is the substitution of the acyl group having 3 to 22 carbon atoms substituting the hydrogen atom of the hydroxyl group of cellulose. Represents degree.)   The optical compensation sheet according to any one of claims 1 to 9, wherein the tilt angle of the liquid crystalline compound on the alignment film side is manipulated by adding the nucleophile to the alignment film. For forming an alignment film containing an aldehyde compound having two or more aldehyde groups and at least one nucleophilic agent having a nucleophilic constant (n) of 5 or more and 10 or less on a transparent support that has been subjected to adhesion imparting treatment in advance. Applying the composition, heating and hardening to form an alignment film; and
The manufacturing method of an optical compensation sheet which has the process of forming the optically anisotropic layer in this order by coating the composition containing a liquid crystalline compound, orienting and polymerizing this liquid crystalline compound.   In the method for producing an optical compensation sheet having an alignment film and an optically anisotropic layer on a transparent support, the alignment film is formed by applying the alignment film-forming composition by a die coater method. Item 11. A method for producing an optical compensation sheet according to any one of Items 1 to 10.   13. The die coater coating method according to claim 12, wherein the land of the tip lip of the slot die is brought close to the surface of the transparent support that is continuously supported by the backup roll, and the coating liquid is applied from the slot of the tip lip. Using a slot die having a land length in the web traveling direction of the tip lip on the transparent support traveling direction side of the slot die in the method of 30 μm or more and 100 μm or less, and when the slot die is set at a coating position, Coating is performed using a coating apparatus installed such that the gap between the tip lip on the opposite side of the web traveling direction and the web is larger by 30 μm or more and 120 μm or less than the gap between the tip lip on the web traveling direction side and the web. The method for producing an optical compensation sheet according to claim 12.   A polarizing plate, wherein a transparent protective film, a polarizing film, and the optical compensation sheet according to any one of claims 1 to 10 are laminated in this order.   The polarizing plate according to claim 14, wherein the transparent protective film of the polarizing plate according to claim 14 is provided with an antireflection film on the air side surface of the protective film.   In a liquid crystal display device comprising a polarizing film and a polarizing plate comprising two transparent protective films disposed on both sides of the polarizing film, the two sheets disposed between the liquid crystal cell and the polarizing plate. A liquid crystal display device, wherein at least one of the transparent protective films is the optical compensation sheet according to any one of claims 1 to 10.   17. The liquid crystal display device according to claim 16, wherein the liquid crystal display device is a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, ECB, and OCB modes.

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