JP2013061372A - Manufacturing method of film patterned retarder, film patterned retarder, and polarizer plate and image display device including the same - Google Patents

Abstract

The present invention provides a method for producing a film-patterned retarder having a high-definition alignment pattern and suppressing a positional deviation of the pattern due to a dimensional change.
A method for producing a film patterned retarder having at least a film and a patterned retarder layer thereon, wherein 1) the film is Tg-100 <T ₁ <Tg (where Tg is a film) 2) a step of heating at T ₁ that satisfies the glass transition point of 2), a step of applying a composition containing liquid crystal as a main component on the surface of the film, and forming a coating film; and 3) A method for producing a film, patterned retarder, comprising the steps of heating a coating film and aligning liquid crystals in this order.
[Selection figure] None

Description

  The present invention relates to a method for producing a film-patterned retarder having a high-definition pattern, which is easy to manufacture and excellent in practicality, and a film-patterned retarder produced thereby, and polarized light having the same The present invention relates to an image display device such as a plate and a stereoscopic image display device.

  There is an increasing demand for patterned retarders used in stereoscopic image display devices. In particular, there is high expectation for a film patterned retarder (hereinafter sometimes referred to as “FPR”) having a patterned retarder layer on a film support, which is excellent in handleability, flexibility, lightness and the like. .

  By the way, the production of a patterned retarder requires a high-definition and fine pattern forming technique corresponding to the pattern of pixels and the like. Conventionally, a configuration of a so-called in-cell type liquid crystal cell having a pattern retardation layer in the liquid crystal cell has been proposed (for example, Patent Document 1), and various patterns are used for forming the pattern retardation layer of the in-cell type liquid crystal cell. Technology is being used.

JP 2006-39327 A

  However, in the production of a conventional so-called in-cell type liquid crystal cell, a rigid glass substrate for the liquid crystal cell is used as a support, and a pattern retardation layer is formed thereon. In FPR, it is necessary to form a fine retardation layer pattern on a flexible film, and there is a problem that the film undergoes dimensional changes during the manufacturing process, resulting in pattern misalignment. If an FPR having a positional deviation is used in a stereoscopic image display device, crosstalk occurs.

An object of the present invention is to solve the above problems.
Specifically, a first object of the present invention is to provide a method for producing a film / patterned retarder having a high-definition alignment pattern and suppressing a positional deviation of the pattern due to a dimensional change.
The second problem of the present invention is to provide a film / patterned retarder in which pattern misalignment due to dimensional change is suppressed, a polarizing plate having the film retarder, and a low-cost and highly visible stereoscopic image display device. is there.

Means for solving the above problems are as follows.
[1] A method for producing a film / patterned retarder having at least a film and a patterned retarder layer thereon, the following 1) to 3)
1) Step of heating the film at T ₁ satisfying Tg−100 <T ₁ <Tg (where Tg is a glass transition point of the film) 2) On the surface of the film, liquid crystal is contained as a main component. A step of applying a composition to form a coating film, and 3) a step of aligning liquid crystals by heating the coating film,
In this order, a method for producing a film-patterned retarder.
[2] The method according to [1], wherein the 1) step is a step of setting the film surface temperature T _1s of the film to Tg−120 ° C. ≦ T _1S ° C ≦ Tg−20 ° C.
[3] The method according to [1] or [2], wherein the step 1) is a step in which the cellulose acylate film is heated to bring the film surface temperature of the film to 80 ° C to 150 ° C.
[4] 1) The method according to any one of [1] to [3], including a step of performing mask exposure after the step.
[5] and the total pitch P ₁ of the mask used to mask exposure, the ratio [Delta] P / P ₁ of the difference [Delta] P between the total pitch P ₂ of the patterned retarder (= P ₁ -P ₂₎ is less than 0.1% The method of [4].
[6] The mask exposure step is a step of forming a pattern alignment film in which first and second alignment control regions each having an alignment ability to align the major axis of the liquid crystal in different directions are alternately arranged. ] Or [5].
[7] 3) The method according to any one of [1] to [6], further including a step of fixing the alignment of the liquid crystal after the step.
[8] A patterned retarder including a first phase difference region and a second phase difference region having mutually different in-plane slow axis directions, wherein the first and second phase difference regions are alternately arranged in the plane. The method according to any one of [1] to [7], which is a method for producing a film-patterned retarder having a layer.
[9] A film / patterned retarder produced by the method of any one of [1] to [8].
[10] A polarizing plate having the film-patterned retarder of [9] and a polarizer.
[11] An image display device having the film patterned retarder according to [9] or the patterned polarizing plate according to [10].

ADVANTAGE OF THE INVENTION According to this invention, it can provide the manufacturing method of the film patterned retarder which has a high-definition orientation pattern and the position shift of the pattern by a dimensional change was suppressed.
Further, according to the present invention, it is possible to provide a film / patterned retarder in which a positional deviation of a pattern due to a dimensional change is suppressed, a polarizing plate having the film retarder, and a stereoscopic image display device with high cost and high visibility. .

It is a cross-sectional schematic diagram of an example of the film patterned retarder which can be manufactured with the method of this invention. It is a top view of an example of the film patterned retarder which can be manufactured with the method of this invention. It is an upper surface schematic diagram of the alignment film which can be used for this invention. It is the schematic which shows an example of the relationship between the patterned retarder layer manufactured by the method of this invention, and a linearly-polarizing film. It is the schematic diagram which showed the cross-sectional schematic diagram of four examples of the film patterned retarder manufactured by the method of this invention as a combination with a liquid crystal display panel part. It is an upper surface schematic diagram of an example of the patterned retarder layer formed in the Example. It is a cross-sectional schematic diagram of a part of the rubber-like flexographic plate used in the examples. It is a cross-sectional schematic diagram of a part of the flexographic printing apparatus used in the examples. It is the upper surface schematic diagram used in order to show the direction of the mask utilized in the Example, and a wire grid polarizer.

  Hereinafter, the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

1. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an FPR, and more specifically, is a method for manufacturing a film patterned retarder having at least a film and a patterned retarder layer thereon. The following 1) to 3)
1) A step of heating the film at T ₁ satisfying Tg−100 <T ₁ <Tg (where Tg is a glass transition point of the film),
2) a step of applying a composition containing liquid crystal as a main component on the surface of the film to form a coating film, and 3) a step of heating the coating film to align the liquid crystal,
In this order, the present invention relates to a method for manufacturing an FPR.

One feature of the method of the present invention is that, before the patterned retarder is formed, the step 1) is carried out, that is, the film used as the support is heat-treated. This heat treatment relaxes the orientation of the main component polymer in the film, stabilizes it in an equilibrium state, and can reduce dimensional changes depending on the heat and / or humidity of the film, thereby forming on it. The positional deviation of the pattern of the patterned optically anisotropic layer can be reduced.
In the present specification, the term “polymer” is used to include both resins and polymers (including both homopolymers and copolymers).

  For example, when mask exposure or mask rubbing is performed on an alignment film or the like for the formation of a patterned retarder, the mask used corresponds to the pixel of the image display device equipped with the patterned retarder. In addition, the width of the opening and the non-opening (referred to herein as “mask pitch”) is precisely adjusted. However, even if mask exposure is performed using a mask with a precisely adjusted pitch, if the film as a support changes in dimensions due to heat or environmental humidity provided during the manufacturing process, Misalignment occurs. In the method of the present invention, since the dimensional change due to heat or the like of the support film is suppressed by performing the above heat treatment, the positional deviation of the pattern can be reduced.

Specifically, according to the production method of the present invention, in the embodiment in which mask exposure or mask rubbing is performed for pattern formation after the step 1), that is, the heat treatment step of the support film, it is used in the step. the total pitch P ₁ of the mask that is, the ratio [Delta] P / P ₁ of the difference [Delta] P (= P ₁ -P ₂₎ between the total pitch P ₂ of the patterned retarder layer, less than 0.1% (preferably 0.09 % Or less, more preferably 0.8% or less). When a support film not subjected to the above heat treatment is used, ΔP / P ₁ exceeds 0.1%, and when used in a stereoscopic image display device, a crosstalk phenomenon may be observed.

Note that the total mask pitch P ₁ refers to the total width of a plurality of openings and non-openings existing in a region to be processed of the mask subjected to processing such as exposure. For example, in an aspect where n openings and n non-openings in a stripe shape with a pitch P exist alternately in the region to be processed, the total pitch is 2 × n × P. Pattern total pitch P ₂ of the de retarder layer is also similar, we shall refer to a total width of the patterned retarder layer formed at a position corresponding to the treated area of the mask.

  Hereinafter, each step of the method of the present invention will be described in detail.

1) In step 1) step, the support _{film, Tg-100 <T 1 <} Tg ( where Tg is heated by T ₁ satisfying the glass transition point is) of the film. By this step, residual strain and the like in the film can be eliminated, the non-equilibrium state can be stabilized and the main component polymer can be relaxed at least partially. By heat treatment, at least a part of the main chain of the polymer may be relaxed, at least a part of the side chain may be relaxed, or at least a part of both may be relaxed. In particular, it is preferable that at least a part of the side chain of the polymer is relaxed in orientation in order to eliminate distortion and the like generated in the amorphous part by heat treatment.
The presence or absence of orientational relaxation of the main component polymer in the film can be confirmed by tracking X-rays or Raman analysis.

1) In the step, the film is heated at T ₁ satisfying Tg−100 ° C. <T ₁ <Tg ° C. (where Tg is the glass transition point of the film). By heating in this range, the orientation relaxation of the main component polymer in the film can be promoted stably. The heating temperature T ₁ is preferably Tg−80 ° C. <T ₁ <Tg−10 ° C. In addition, even if it is a case where the presence or absence of the orientation relaxation of a main component polymer cannot be confirmed with the said analysis method, the effect of this invention is acquired by heat-processing at the temperature within this range. In addition, the glass transition point of a film can be known by DSC measurement.

The film surface temperature T _1s of the film is preferably Tg−120 ° C. ≦ T _1S ° C ≦ Tg−20 ° C. by performing the heat treatment at the temperature T ₁ , and Tg−100 ° C. ≦ T _1S ° C ≦ Tg− More preferably, the temperature is 30 ° C. For example, since the Tg of cellulose acylate containing cellulose acylate as a main component is generally about 160 to 200 ° C., in the embodiment using a cellulose acylate film as a support film, 1) This is a step of heating the rate film to bring the film surface temperature of the film to 80 to 150 ° C. (more preferably 100 to 130 ° C.).

  1) The time t during which the heat treatment in the step is performed is not particularly limited, but in general, 1 minute ≦ t ≦ 60 minutes is preferable, and 2 minutes ≦ t ≦ 10 minutes is particularly preferable.

  1) Implementation of the process may be utilized to form other layers on the film. Specifically, the functional layer may be formed by drying the coating film formed on the film by performing the heat treatment in step 1). An example of the functional layer is an alignment film that can control the alignment of the liquid crystal applied on the film in step 2). Needless to say, the alignment film may be formed on the film 1) before the step, or after the step 1) and before the step 2) separately from the execution of the step 1).

  For example, 1) Before carrying out the process, the coating liquid containing the alignment film material is applied to the film surface to form a coating film. 1) The solvent in the coating film is dried by heat treatment in the process. -An alignment film can be formed by removing.

  Moreover, 1) A process may be implemented simultaneously with the surface treatment with respect to a film. The film may be subjected to a surface treatment for improving the adhesion with the patterned retarder layer formed thereon. When the surface treatment to be employed includes a heating step, step 1) may be performed simultaneously with the heating step. The 1) step is, for example, a drying step after alkali saponification treatment, a surface film processing step such as an antireflection layer to be described later, and the like, and may be performed simultaneously with these steps.

  The method of the present invention requires a pattern forming step for constructing a patterned retarder pattern. An example of the pattern forming process is a process using a mask having an opening and a non-opening such as mask exposure or mask rubbing. The treatment using the mask is preferably performed on the alignment film. For example, after forming the alignment film on the film surface, simultaneously with 1) step, before 1) step, or after 1) step and before 2) step, 2) before the step It is preferable to perform a process using a mask such as mask exposure or mask rubbing on the film to form a pattern alignment film. One example of the pattern alignment film is that first and second alignment control regions each having an alignment control ability to align the major axis (sometimes referred to as a slow axis) of liquid crystal molecules in mutually different (for example, orthogonal) directions alternately. It is the arranged pattern alignment film.

  As the mask, a mask in which the pitches of the openings and the non-openings are precisely adjusted according to the pixels of the mounted image display device is used. In the present invention, the change in the dimension of the film during the subsequent steps is suppressed by performing the step 1). Therefore, the pattern formed by the process using the mask is maintained in the subsequent process.

There are no particular restrictions on the conditions of mask exposure for forming the pattern alignment film. Depending on the mechanism of pattern alignment film formation, preferred exposure conditions will also vary. In an embodiment in which a pattern alignment film is formed by utilizing decomposition of a photoacid generator described later, the photoacid generator is decomposed by mask ultraviolet exposure to generate an acidic compound. Since generation and diffusion of an acidic compound occur with the decomposition of the photoacid generator, ultraviolet rays are preferably used for irradiation under a photomask, and unpolarized ultraviolet rays are more preferably used. Preferably has a peak at 200~250nm the irradiation wavelength, it is preferable to use a UV-C light source, the exposure amount is preferably 5~1000mJ / cm ² approximately, 5 to 100 mJ / cm ² about More preferably, it is about 5-50 mJ / cm < ² >. If the exposure amount is too small, a pattern cannot be formed. On the other hand, when the exposure amount is too large, the pattern resolution decreases due to the diffusion of the acidic compound. In order to improve the pattern resolution, exposure at room temperature is preferable.
The light irradiation conditions can be appropriately set according to the composition of the alignment film composition and the like, and are not limited to the above conditions.

  The pattern alignment film may be a photo-alignment film, and in this embodiment, linearly polarized ultraviolet rays are used for mask exposure.

  The pattern alignment film may be formed by performing a mask rubbing process using a mask.

  An example of the mask used is a mask in which striped openings and non-openings are alternately arranged. The width (pitch) of the opening and the non-opening is determined according to the configuration of the pixels of the mounted image display device. Generally, the width of each stripe is 100 to 1000 μm.

2) Step In the step 2), a coating film is formed by applying a composition containing liquid crystal as a main component on the surface of the film. The step 2) is preferably performed after an alignment film (more preferably a pattern alignment film) is formed.

  The composition containing liquid crystal is preferably prepared as a coating solution. There is no restriction | limiting in particular about the solvent used for preparation of a coating liquid, The 1 type, or 2 or more types of mixed solvent of the organic solvent in which a liquid crystal is soluble can be used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

  There are no particular restrictions on the coating method, curtain coating method, dip coating method, spin coating method, print coating method, spray coating method, slot coating method, roll coating method, slide coating method, blade coating method, gravure coating method, A known coating method such as a wire bar method may be used.

3) Step 3) In the step 3), the coating film is heated to align the liquid crystal. The heating temperature T ₃ at this time is determined according to the liquid crystal phase transition temperature and the isotropic phase transition temperature of the liquid crystal used. Generally, it is 50-150 degreeC, It is preferable that it is 70-140 degreeC, and it is more preferable that it is 80-130 degreeC. Incidentally, 1) in relation to the heating temperature T ₁ of the process, T ₃ is preferably satisfies the T ₃ ≦ T _1. 3) It is preferable that the heating step at a temperature exceeding T ₁ is not performed in any step until the patterned retarder layer is formed, not limited to the heating temperature T ₃ in the step. For example, after the step 1), a heat treatment may be performed when the surface treatment of the film, the formation of the alignment film, or the like is performed, but it is preferably performed at a heating temperature T ₁ ° C. of the step 1). 2) Although heat treatment may be performed in the process, the heating temperature is also less than T ₁ ° C.

  In the step 3), the liquid crystal is aligned to form, for example, a pattern composed of a plurality of retardation regions in which at least one of the in-plane slow axis and the retardation is different from each other. An example includes a patterned retarder that includes a first phase difference region and a second phase difference region that have mutually different in-plane slow axis directions, and the first and second phase difference regions are alternately arranged in a plane. Is a layer. The patterned retarder layer is a liquid crystal on a pattern alignment film in which first and second alignment control regions each having an alignment control ability to align the major axis of the liquid crystal in different (for example, orthogonal) directions are alternately arranged. It can be formed by orienting. For example, the liquid crystal is aligned so that the slow axis of the liquid crystal is perpendicular and parallel to the rubbing direction of the pattern rubbing alignment film. Thereby, the directions of the in-plane slow axes of the first and second retardation regions are determined, and the first and second retardation regions having in-plane slow axes perpendicular to each other are formed. Furthermore, the optical characteristics (Re and Rth) of the first and second retardation regions are determined by the alignment state of the liquid crystal. The patterned retarder layer is preferably a λ / 4 plate, that is, an optically anisotropic layer having a function of converting linearly polarized light into circularly polarized light. There are various alignment states of the liquid crystal having a function as a λ / 4 plate. An example is an alignment state in which the slow axis (molecular long axis) of the rod-like liquid crystal compound is horizontally aligned on the layer surface. Another example is an alignment state in which the disc surface of the discotic liquid crystal is aligned perpendicular to the layer surface. The vertical alignment state of the discotic liquid crystal is more preferable.

  Of course, when a process using a mask such as mask exposure is performed on a film containing liquid crystal by the action of liquid crystal or an additive used therewith, a patterned retarder layer can be formed. There is also. Or, in order to form a plurality of retardation regions such as the first and second retardation regions, a plurality of liquid crystal compositions in which liquid crystals and / or additives are different from each other or their content ratios are different from each other are used. A patterned retarder layer may be formed. In any aspect, 1) performing the process suppresses the dimensional change of the film in the subsequent process, and thus pattern formation as designed is possible.

  3) It is preferable to fix the alignment of the liquid crystal after the step. In order to suppress fluctuations in the optical properties of the patterned retarder layer, fixing is preferably performed with the formation of a chemical bond, and is preferably performed by a polymerization reaction or a crosslinking reaction. Therefore, the composition used in step 3) is preferably a curable composition having polymerizability or crosslinkability. It is also preferred that the liquid crystal has a polymerizable group or a crosslinkable group.

  It is preferable to fix the alignment of the liquid crystal by carrying out a polymerization reaction of the curable composition. The polymerization reaction used may be a photopolymerization reaction or a thermal polymerization reaction. The photopolymerization reaction is preferable in terms of easy control. That is, the curable composition preferably contains a photopolymerization initiator that enables a photopolymerization reaction.

For the light irradiation performed for fixing the alignment of the liquid crystal, for example, ultraviolet rays are used. Irradiation energy is preferably ^{10mJ / cm 2 ~10J / cm 2} , further preferably 25~800mJ / cm ^2. Illuminance is preferably 10 to 1,000 / cm ^2, more preferably 20 to 500 mW / cm ^2, further preferably 40~350mW / cm ^2. The irradiation wavelength preferably has a peak at 250 to 450 nm, and more preferably has a peak at 300 to 410 nm. In order to accelerate the photopolymerization reaction, light irradiation may be performed under an inert gas atmosphere such as nitrogen or under heating conditions. The light source is preferably a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp) or short arc discharge lamp (ultra-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Used.

Examples of the method for forming the patterned retarder layer include the following modes.
The first aspect uses a plurality of actions that affect the alignment control of the liquid crystal, and then eliminates any action by an external stimulus (such as heat treatment) to make the predetermined alignment control action dominant. It is. For example, the liquid crystal is brought into a predetermined alignment state by the combined action of the alignment control ability by the alignment film and the alignment control ability of the alignment control agent added to the liquid crystal composition, and one phase difference region is fixed by fixing it. After forming, by external stimulus (heat treatment, etc.), one of the actions (for example, the action by the alignment control agent) disappears, and the other orientation control action (the action by the alignment film) becomes dominant, thereby other orientations. The state is realized and fixed to form the other phase difference region. For example, a predetermined pyridinium compound or imidazolium compound described later is unevenly distributed on the hydrophilic polyvinyl alcohol alignment film surface because the pyridinium group or imidazolium group is hydrophilic. In particular, if the pyridinium group is further substituted with an amino group that is a substituent of an acceptor of a hydrogen atom, intermolecular hydrogen bonds are generated with polyvinyl alcohol, and are unevenly distributed on the surface of the alignment film at a higher density. At the same time, due to the effect of hydrogen bonding, the pyridinium derivative is aligned in the direction orthogonal to the main chain of polyvinyl alcohol, so that the orthogonal alignment of the liquid crystal is promoted relative to the rubbing direction. The predetermined pyridinium derivatives described later have a plurality of aromatic rings in the molecule, so that a strong intermolecular π-π interaction occurs between the liquid crystal, particularly the discotic liquid crystal, and the orientation of the discotic liquid crystal. Induces orthogonal orientation near the film interface. In particular, when a hydrophobic aromatic ring is connected to a hydrophilic pyridinium group, it also has an effect of inducing vertical alignment due to the hydrophobic effect. However, the effect is that when heated above a certain temperature, the hydrogen bond is broken, the uneven distribution and density on the surface of the alignment film such as the pyridinium compound are lowered, and the action disappears. As a result, the liquid crystal is aligned by the regulating force of the rubbing alignment film itself, and the liquid crystal is in a parallel alignment state. Details of this method are described in Japanese Patent Application No. 2010-141346, the contents of which are incorporated herein by reference.
In this embodiment, mask exposure is performed on a film containing liquid crystal in order to fix the alignment state.

In the second aspect, a pattern alignment film is used. In this embodiment, pattern alignment films having different alignment control capabilities are formed, and a liquid crystal composition is disposed thereon to align the liquid crystal. The alignment of the liquid crystal is regulated by the respective alignment control ability of the pattern alignment film, thereby achieving different alignment states. By fixing the respective alignment states, the patterns of the first and second retardation regions are formed according to the alignment film pattern. The pattern alignment film can be formed using a printing method, mask rubbing for the rubbing alignment film, mask exposure for the photo alignment film, or the like. Alternatively, the alignment film can be formed uniformly, and an additive (for example, the onium salt or the like) that affects the alignment control ability is separately printed in a predetermined pattern to form the pattern alignment film. A method using a printing method is preferable in that large-scale equipment is not required and manufacturing is easy. Details of this method are described in Japanese Patent Application No. 2010-173077, the contents of which are incorporated herein by reference.
In this aspect, for example, processing such as mask exposure using a mask is performed on the alignment film.

Moreover, you may use the 1st and 2nd aspect together. An example is an example in which a photoacid generator is added to the alignment film. In this example, a photoacid generator is added to the alignment film, and pattern exposure exposes a region where the photoacid generator is decomposed to generate an acidic compound and a region where no acid compound is generated. The photoacid generator remains almost undecomposed in the unirradiated portion, and the interaction between the alignment film material, the liquid crystal, and the alignment control agent added as required dominates the alignment state, and the liquid crystal has its slow axis. Is oriented in a direction perpendicular to the rubbing direction. When the alignment film is irradiated with light and an acidic compound is generated, the interaction is no longer dominant, the rubbing direction of the rubbing alignment film dominates the alignment state, and the liquid crystal has its slow axis parallel to the rubbing direction. Parallel orientation. As the photoacid generator used for the alignment film, a water-soluble compound is preferably used. Examples of photoacid generators that can be used include Prog. Polym. Sci. , 23, 1485 (1998). As the photoacid generator, pyridinium salts, iodonium salts and sulfonium salts are particularly preferably used. Details of this method are described in Japanese Patent Application No. 2010-289360, the contents of which are incorporated herein by reference.
In this embodiment, mask exposure is performed on the alignment film.

  The aspect of the pattern forming method is an example, and is not limited to the above aspect.

  After forming the patterned retarder layer or before forming it, a step for stacking other functional layers may be performed. Examples of other functional layers include a polarizing film, a hard coat layer, and an antireflection layer. A laminated film in which these layers are formed on a film may be produced and bonded to a film / patterned retarder produced by the above method. In addition, after forming the patterned retarder layer or before forming, the functional layer is formed on the back surface of the film used as a support (the surface opposite to the surface on which the patterned retarder layer is formed). You may form by bonding or application | coating. Further, after the patterned retarder layer is formed, it may be formed directly on the surface of the patterned retarder layer by bonding or coating.

  Next, various materials that can be used in the method of the present invention will be described.

Support film:
The support film is not particularly limited as long as it contains a polymer (meaning including both a resin and a polymer) as a main component. A polymer excellent in optical performance transparency, mechanical strength, thermal stability, moisture shielding property, isotropy and the like is preferable. Examples include polycarbonate polymers, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, acrylic polymers such as polymethyl methacrylate, and styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin). Polyolefins such as polyethylene and polypropylene, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethersulfone polymers , Polyether ether ketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, or polymers mixed with the above polymers Take an example. The polymer film of the present invention can also be formed as a cured layer of an ultraviolet-curable or thermosetting resin such as acrylic, urethane, acrylic urethane, epoxy, or silicone.

  As a material for forming the transparent support, a thermoplastic norbornene resin can be preferably used. Examples of the thermoplastic norbornene-based resin include ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., and ARTON manufactured by JSR Corporation.

In addition, as a material for forming the transparent support, a cellulose polymer represented by triacetyl cellulose (hereinafter referred to as cellulose acylate), which has been conventionally used as a transparent protective film of a polarizing plate, is preferably used. it can.
Hereinafter, cellulose acylate will be described in detail mainly as an example of the transparent support, but it is obvious that the technical matters can be applied to other polymer films as well.

  Examples of cellulose as a cellulose acylate raw material include cotton linter and wood pulp (hardwood pulp, softwood pulp). Cellulose acylate obtained from any raw material cellulose can be used, and in some cases, a mixture may be used. Details of these raw material celluloses are, for example, the plastic material course (17) Fibrous resin (manufactured by Marusawa and Uda, Nikkan Kogyo Shimbun, published in 1970) and the Japan Institute of Technology Open Technical Report 2001-1745 (7-8 However, the present invention is not limited to the description.

  Cellulose acylate is obtained by acylating a hydroxyl group of cellulose, and the substituent can be any acetyl group having 2 carbon atoms in the acyl group to those having 22 carbon atoms. In the cellulose acylate of the present invention, the degree of substitution of cellulose with a hydroxyl group is not particularly limited, but the degree of binding of acetic acid and / or a fatty acid having 3 to 22 carbon atoms substituted with a hydroxyl group of cellulose is measured and substituted by calculation. You can get a degree. As a measuring method, it can carry out according to ASTM D-817-91.

  The degree of substitution of cellulose with a hydroxyl group is not particularly limited, but the degree of acyl substitution with a hydroxyl group of cellulose is preferably 2.50 to 3.00. Furthermore, the degree of substitution is preferably 2.75 to 3.00, and more preferably 2.85 to 3.00.

  Among the acetic acid and / or the fatty acid having 3 to 22 carbon atoms substituted for the hydroxyl group of cellulose, the acyl group having 2 to 22 carbon atoms may be an aliphatic group or an aromatic group, and is not particularly limited. It may be a mixture of more than one type. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. These preferred acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, iso-butanoyl, t-butanoyl, cyclohexanecarbonyl, Examples include oleoyl, benzoyl, naphthylcarbonyl, and cinnamoyl groups. Among these, acetyl, propionyl, butanoyl, dodecanoyl, octadecanoyl, t-butanoyl, oleoyl, benzoyl, naphthylcarbonyl, cinnamoyl and the like are preferable, and acetyl, propionyl and butanoyl are more preferable.

Among the acyl substituents substituted on the hydroxyl group of cellulose described above, in the case of substantially consisting of at least two types of acetyl group / propionyl group / butanoyl group, the degree of substitution is 2.50 to 3.00. The optical anisotropy of the cellulose acylate film can be reduced.
A more preferable degree of acyl substitution is 2.60 to 3.00, and more preferably 2.65 to 3.00. In addition, when the acyl substituent substituted for the hydroxyl group of cellulose consists only of acetyl groups, in addition to being able to reduce the optical anisotropy of the film, it is further compatible with additives and soluble in organic solvents to be used. From the viewpoint, the degree of substitution is preferably 2.80 to 2.99, more preferably 2.85 to 2.95.

The degree of polymerization of cellulose acylate is preferably 180 to 700 in terms of viscosity average degree of polymerization. In cellulose acetate, 180 to 550 is more preferable, 180 to 400 is further preferable, and 180 to 350 is particularly preferable. When the degree of polymerization is too high, the viscosity of the cellulose acylate dope solution becomes high, and film production becomes difficult due to casting. If the degree of polymerization is too low, the strength of the produced film will decrease. 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. 18, No. 1, pages 105-120, 1962). This is described in detail in JP-A-9-95538.
Further, 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 mass 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 3.0, more preferably 1.0 to 2.0, and most preferably 1.0 to 1.6. preferable.

  When the low molecular component is removed, the average molecular weight (degree of polymerization) increases, but the viscosity becomes lower than that of normal cellulose acylate, which is useful. Cellulose acylate having a small amount of low molecular components can be obtained by removing low molecular components from cellulose acylate synthesized by a usual method. The removal of the low molecular component can be carried out by washing the cellulose acylate with an appropriate organic solvent. In addition, when manufacturing a cellulose acylate with few low molecular components, it is preferable to adjust the sulfuric acid catalyst amount in an acetylation reaction to 0.5-25 mass parts with respect to 100 mass parts of cellulose. When the amount of the sulfuric acid catalyst is within the above range, cellulose acylate that is preferable in terms of molecular weight distribution (uniform molecular weight distribution) can be synthesized. When used in the production of the cellulose acylate of the present invention, the water content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly 0.7% by mass or less. . In general, cellulose acylate contains water and is known to have a moisture content of 2.5 to 5% by mass. In order to obtain the moisture content of cellulose acylate, it is necessary to dry the cellulose acylate, and the method is not particularly limited as long as the desired moisture content is achieved. The method for synthesizing these cellulose acylates of the present invention is described in detail on pages 7 to 12 in the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society for Invention). .

  Cellulose acylate can be used by mixing two or more different types of cellulose acylate as long as the substituent, substitution degree, polymerization degree, molecular weight distribution and the like are within the above-mentioned ranges.

For the production of a film used as a support, together with cellulose acylate, various additives (for example, compounds that reduce optical anisotropy, wavelength dispersion adjusting agents, fine particles, plasticizers, UV inhibitors, deterioration inhibitors, Release agents, optical property modifiers, etc.) can be used, and these are described below. Moreover, the addition time may be any in the dope preparation process (the preparation process of the cellulose acylate solution), but a step of adding and preparing an additive may be performed at the end of the dope preparation process.
By adjusting the addition amount of these additives, a cellulose acylate film satisfying 0 ≦ Re (550) ≦ 10 can be produced. By using the film as a support, the optical properties of the support can be improved. The Re of all the first and second retardation regions contained in the optical film of the present invention can be in the range of 110 nm ≦ Re (550) ≦ 165 nm with little influence. The Re value is preferably 120 ≦ Re (550) ≦ 145, and particularly preferably 130 ≦ Re (550) ≦ 145.

  Further, in relation to the optically anisotropic layer described later, since the total of Rth of the transparent support and Rth of the optically anisotropic layer (λ / 4 plate) satisfies | Rth | ≦ 20 nm, the transparent support Preferably satisfies −150 nm ≦ Rth (630) ≦ 100 nm.

It is a preferable embodiment that contains at least one compound that lowers the optical anisotropy of the cellulose acylate film.
The compound that reduces the optical anisotropy of the cellulose acylate film will be described. Optical anisotropy can be reduced by using a compound that suppresses the orientation of cellulose acylate in the film in the plane and in the film thickness direction. The compound that lowers the optical anisotropy is sufficiently compatible with cellulose acylate, and it is advantageous that the compound itself does not have a rod-like structure or a planar structure. Specifically, when a plurality of planar functional groups such as aromatic groups are provided, a structure having these functional groups in a non-planar rather than the same plane is advantageous.

In order to produce a cellulose acylate film having a low retardation, among the compounds that reduce the optical anisotropy by inhibiting the cellulose acylate in the film from being oriented in the plane and in the film thickness direction as described above. A compound having an octanol-water partition coefficient (log P value) of 0 to 7 is preferred. A compound having a log P value of more than 7 is poor in compatibility with cellulose acylate, and tends to cause film turbidity or powder blowing. In addition, a compound having a log P value of less than 0 has high hydrophilicity, and thus may deteriorate the water resistance of the cellulose acetate film. A more preferable range for the logP value is 1 to 6, and a particularly preferable range is 1.5 to 5.
The octanol-water partition coefficient (log P value) can be measured by a flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (log P value) can be estimated by a computational chemical method or an empirical method instead of the actual measurement. As a calculation method, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29,). 163 (1989).), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984).) And the like are preferably used, but the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987). When the log P value of a certain compound varies depending on the measurement method or calculation method, it is preferable to determine whether or not the compound is within the range by the Crippen's fragmentation method. In addition, the value of logP described in this specification is determined by the Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)).

The compound that decreases the optical anisotropy may or may not contain an aromatic group. The compound that reduces the optical anisotropy preferably has a molecular weight of 150 or more and 3000 or less, more preferably 170 or more and 2000 or less, and particularly preferably 200 or more and 1000 or less. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.
The compound that reduces optical anisotropy is preferably a liquid at 25 ° C. or a solid having a melting point of 25 to 250 ° C., more preferably a liquid at 25 ° C. or a melting point of 25 to 200. C solid. Moreover, it is preferable that the compound which reduces optical anisotropy does not volatilize in the process of dope casting and drying of cellulose acylate film production.
The amount of the compound that reduces optical anisotropy is preferably 0.01 to 30% by mass, more preferably 1 to 25% by mass, and 5 to 20% by mass with respect to cellulose acylate. It is particularly preferred.
The compound that decreases the optical anisotropy may be used alone, or two or more compounds may be mixed and used in an arbitrary ratio.
The timing for adding the compound for reducing the optical anisotropy may be any time during the dope preparation process, or may be performed at the end of the dope preparation process.

  The compound that reduces the optical anisotropy is such that the average content of the compound in the portion from the surface on at least one side to 10% of the total film thickness is the average content of the compound in the center of the cellulose acylate film. 80-99% of the rate. The amount of the compound present can be determined, for example, by measuring the amount of the compound at the surface and in the center by a method using an infrared absorption spectrum described in JP-A-8-57879.

  Specific examples of the compound that reduces the optical anisotropy of the cellulose acylate film include, for example, the compounds described in [0035] to [0058] of JP-A-2006-199855, but are limited to these compounds. Is not to be done.

It is desirable to add an ultraviolet (UV) absorber to the film.
Among these, UV absorbers are compounds that have absorption in the ultraviolet region of 200 to 400 nm and reduce both | Re (400) -Re (700) | and | Rth (400) -Rth (700) | Preferably, it is good to use 0.01-30 mass% with respect to cellulose acylate solid content.

  In recent years, liquid crystal display devices such as televisions, notebook personal computers, and mobile portable terminals have been required to have excellent transmittance of optical members used in liquid crystal display devices in order to increase luminance with less power. In that respect, a compound having absorption in the ultraviolet region of 200 to 400 nm and reducing | Re (400) -Re (700) | and | Rth (400) -Rth (700) | When it is added, it is required that the spectral transmittance is excellent. In the cellulose acylate film of the present invention, the spectral transmittance at a wavelength of 380 nm is preferably 45% to 95%, and the spectral transmittance at a wavelength of 350 nm is preferably 10% or less.

  The UV absorber preferably has a molecular weight of 250 to 1000 from the viewpoint of volatility. More preferably, it is 260-800, More preferably, it is 270-800, Most preferably, it is 300-800. A specific monomer structure may be used as long as these molecular weights are within the range, and an oligomer structure or a polymer structure in which a plurality of the monomer units are bonded may be used.

  It is preferable that the UV absorber does not volatilize during the dope casting and drying process for producing the cellulose acylate film.

  Specific examples of the UV absorber for the cellulose acylate film include the compounds described in JP-A-2006-199855, [0059] to [0135].

  It is preferable to add fine particles as a matting agent to the cellulose acylate film. The fine particles used in the present invention include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Mention may be made of magnesium and calcium phosphates. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable. The silicon dioxide fine particles preferably have a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more. Those having an average primary particle size as small as 5 to 16 nm are more preferred because they can reduce the haze of the film. The apparent specific gravity is preferably 90 to 200 g / liter or more, and more preferably 100 to 200 g / liter or more. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.

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

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

  Among these, Aerosil 200V and Aerosil R972V are fine particles of silicon dioxide having a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and the coefficient of friction is maintained while keeping the turbidity of the optical film low. It is particularly preferable because it has a great effect of reducing the effect.

In order to obtain a cellulose acylate film having particles having a small secondary average particle size in the present invention, several methods are conceivable when preparing a fine particle dispersion. For example, a fine particle dispersion prepared by stirring and mixing a solvent and fine particles is prepared in advance, and this fine particle dispersion is added to a small amount of a cellulose acylate solution separately prepared and stirred and dissolved. Further, a main cellulose acylate solution (dope solution) There is a way to mix. This method is a preferred preparation method in that the dispersibility of the silicon dioxide fine particles is good and the silicon dioxide fine particles are more difficult to reaggregate. In addition, after adding a small amount of cellulose ester to the solvent and dissolving with stirring, add the fine particles to this and disperse with a disperser to make this fine particle additive solution, and mix this fine particle additive solution with the dope solution using an in-line mixer. There is also a way to do it. Although not limited to these methods, the concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 15 to 20% by mass. Most preferred. A higher dispersion concentration is preferable because the liquid turbidity with respect to the added amount is lowered, and haze and aggregates are improved. The addition amount of the matting agent fine particles in the final cellulose acylate dope solution is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, more preferably 0.08 to 0.16 g per m ^3. Is most preferred.

  The solvent used is preferably lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like. Although it does not specifically limit as solvents other than a lower alcohol, It is preferable to use the solvent used at the time of film forming of a cellulose ester.

  For the cellulose acylate film, in addition to the compound that optically reduces anisotropy and the UV absorber, various additives (for example, a plasticizer, an ultraviolet ray inhibitor, a deterioration inhibitor, and a release agent) depending on the application. , Infrared absorbers, etc.), which may be solid or oily. That is, the melting point and boiling point are not particularly limited. For example, mixing of ultraviolet absorbing material at 20 ° C. or lower and 20 ° C. or higher, and similarly, mixing of a plasticizer is described in, for example, JP-A-2001-151901. Furthermore, as an infrared absorber, it describes in Unexamined-Japanese-Patent No. 2001-194522, for example. Further, the addition time may be any time in the dope production process, but it is preferable to add an additive at the end of the dope production process. Furthermore, the amount of each additive added is not particularly limited as long as the function is exhibited. Moreover, when a cellulose acylate film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ. For example, although it describes in Unexamined-Japanese-Patent No. 2001-151902 etc., these are techniques conventionally known. For these details, materials described in detail on pages 16 to 22 in the Japan Institute of Invention Disclosure Technical Bulletin (Public Technical No. 2001-1745, published on March 15, 2001, Japan Institute of Invention) are preferably used.

  As for the plasticizer, some of the examples described later do not have a plasticizer added, but compounds that optically reduce anisotropy are compounds that exert an effect as a plasticizer. It goes without saying that in some cases it is not necessary to add a plasticizer.

  The cellulose acylate film is preferably produced by a solution casting method using a cellulose acylate solution. The method for dissolving the cellulose acylate solution (dope) is not particularly limited, and may be room temperature, and further, a cooling dissolution method or a high temperature dissolution method, and further a combination thereof. Regarding the preparation of the cellulose acylate solution, and further the steps of solution concentration and filtration accompanying the dissolving step, 22 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Institute of Invention). Production processes described in detail on pages 25 to 25 are preferably used.

  The dope transparency of the cellulose acylate solution is preferably 85% or more. More preferably, it is 88% or more, and more preferably 90% or more. In the present invention, it was confirmed that various additives were sufficiently dissolved in the cellulose acylate dope solution. As a specific method for calculating the dope transparency, the dope solution was poured into a 1 cm square glass cell, and the absorbance at 550 nm was measured with a spectrophotometer (UV-3150, Shimadzu Corporation). Only the solvent was measured in advance as a blank, and the transparency of the cellulose acylate solution was calculated from the ratio with the absorbance of the blank.

As the method and equipment for producing the cellulose acylate film, a solution casting film forming method and a solution casting film forming apparatus used for producing a conventional cellulose triacetate film are used. The dope (cellulose acylate solution) prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation. The dope is sent from the dope discharge port to the pressure die through a pressure metering gear pump capable of delivering a constant amount of liquid with high accuracy, for example, by the number of rotations, and the dope is run endlessly from the die (slit) of the pressure die. The dry-dried dope film (also referred to as web) is peeled off from the metal support at a peeling point that is uniformly cast on the metal support and substantially rounds the metal support. The both ends of the obtained web are sandwiched between clips, transported by a tenter while holding the width and dried, and then the obtained film is mechanically transported by a roll group of a drying device, dried, and then rolled by a winder. Wind up to a predetermined length. The combination of the tenter and the roll group dryer varies depending on the purpose. In the solution casting film forming method used for the functional protective film as an optical member for an electronic display, which is the main use of the cellulose acylate film of the present invention, in addition to the solution casting film forming apparatus, the undercoat layer In many cases, a coating apparatus is added for surface processing of a film such as an antistatic layer, an antihalation layer, or a protective layer. These are described in detail on pages 25 to 30 in the Japan Society for Invention and Innovation Technical Report (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Inventions). Including), metal support, drying, peeling and the like, and can be preferably used in the present invention.
Moreover, 10-120 micrometers is preferable, as for the thickness of a cellulose acylate film, 20-100 micrometers is more preferable, and 30-90 micrometers is still more preferable.

Patterned retarder layer (patterned optically anisotropic layer):
In the present invention, examples of the liquid crystal that can be used as the main raw material for the patterned retarder layer (patterned optically anisotropic layer) include rod-like liquid crystals and discotic liquid crystals. The discotic liquid crystal having is more preferable.
Examples of the rod-like liquid crystal include Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. Nos. 4,683,327, 5,622,648 and 5,770,107, World Patents (WO) 95/22586, 95/24455. No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, No. 7-110469, No. 11-80081, No. 11-513019 And compounds described in each publication and specification such as Japanese Patent Application No. 2001-64627.

The low molecular rod-like liquid crystal compound is preferably a compound represented by the following general formula (X).
Formula (X)
^{Q 1 -L 1 -Cy 1 -L 2} - (Cy 2 -L 3) n -Cy 3 -L 4 -Q 2
In the formula, Q ¹ and Q ² each independently represent a polymerizable group, L ¹ and L ⁴ each independently represent a divalent linking group, and L ² and L ³ each independently represent a single bond or a divalent group. Represents a linking group, Cy ¹ , Cy ² and Cy ³ each independently represent a divalent cyclic group, and n is 0, 1 or 2.

In the formula, Q ¹ and Q ² are each independently a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction.

As the discotic liquid crystal that can be used as the main raw material of the optically anisotropic layer of the present invention, a compound having a polymerizable group is preferable as described above.
As the discotic liquid crystal, a compound represented by the following general formula (I) is preferable.
Formula (I): D (-LHQ) _n
In the formula, D is a discotic core, L is a divalent linking group, H is a divalent aromatic ring or heterocyclic ring, Q is a group containing a polymerizable group, and n is 3 to 3 Represents an integer of 12.

  The discotic core (D) is preferably a benzene ring, naphthalene ring, triphenylene ring, anthraquinone ring, truxene ring, pyridine ring, pyrimidine ring, or triazine ring, and particularly a benzene ring, triphenylene ring, pyridine ring, pyrimidine ring, or triazine ring. preferable.

  L is preferably a divalent linking group selected from the group consisting of * —O—CO—, * —CO—O—, * —CH═CH—, * —C≡C—, and combinations thereof. Particularly preferred is a divalent linking group containing at least one of CH═CH— and * —C≡C—. Here, * represents a position bonded to D in the general formula (I).

  As the aromatic ring, H is preferably a benzene ring or a naphthalene ring, particularly preferably a benzene ring. As the heterocyclic ring, a pyridine ring and a pyrimidine ring are preferable, and a pyridine ring is particularly preferable. H is particularly preferably an aromatic ring.

The polymerization reaction of the polymerizable group possessed by Q is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Of these, (meth) acrylate groups and epoxy groups are preferred.
Q may contain a linking group for linking H and a polymerizable group. Examples of the linking group include * -O-CO-, * -CO-O-, * -CH = CH-, * -C≡C-, an alkylene group having 1 to 20 carbon atoms (provided that one carbon atom or two or more carbon atoms not adjacent to each other may be replaced by an oxygen atom), and combinations thereof are included.

The discotic liquid crystal represented by the general formula (I) is represented by the following general formula (II) or (III)
The discotic liquid crystal represented by the formula is particularly preferred.

    In the formula, L, H and Q have the same meanings as L, H and Q in the general formula (I), respectively, and preferred ranges thereof are also the same.

In the formula, Y ¹ , Y ² , and Y ³ are synonymous with Y ¹¹ , Y ¹² , and Y ¹³ in the general formula (IV) described later, and their preferred ranges are also the same. Further, L ¹ , L ² , L ³ , H ¹ , H ² , H ³ , R ¹ , R ² , and R ³ are also L ¹ , L ² , L ³ , H ¹ in the general formula (IV) described later. , H ² , H ³ , R ¹ , R ² , R ³ , and their preferred ranges are also the same.

As described later, as represented by the general formula (I), (II), or (III), the discotic liquid crystal having a plurality of aromatic rings in the molecule is used as an alignment control agent. Since an intermolecular π-π interaction occurs with an onium salt such as a pyridinium compound or an imidazolium compound, vertical alignment can be realized. In particular, for example, in the general formula (II), when L is a divalent linking group containing at least one of * —CH═CH— or * —C≡C—, and the general formula In (III), when a plurality of aromatic rings and heterocycles are linked by a single bond, the free rotation of the bond is strongly constrained by the linking group, thereby maintaining the linearity of the molecule. As a result, stronger intermolecular π-π interaction occurs and stable vertical alignment can be realized.

  As the discotic liquid crystal, a compound represented by the following general formula (IV) is preferable.

In the formula, Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine group or a nitrogen atom which may be substituted.

When Y ¹¹ , Y ¹² and Y ¹³ are methine, the hydrogen atom of methine may be replaced by a substituent. Examples of the substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom, and A cyano group can be mentioned as a preferred example. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom, and a cyano group are more preferable.
Y ¹¹ , Y ¹² and Y ¹³ are all preferably methine, and more preferably unsubstituted, from the viewpoint of ease of synthesis of the compound and cost.

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

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

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

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

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

In the general formula ^{(I), H 1, H} 2 and H ³ represent each group independently the general formula (IV-A) or (IV-B).

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

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

一般式（IV−Ｂ）中、ＹＢ¹及びＹＢ²は、それぞれ独立にメチン又は窒素原子を表し；
ＸＢは、酸素原子、硫黄原子、メチレン又はイミノを表し；
＊は上記一般式（IV）におけるＬ¹〜Ｌ³側と結合する位置を表し；
＊＊は上記一般式（IV）におけるＲ¹〜Ｒ³側と結合する位置を表す。

In the general formula (IV-B), YB ¹ and YB ² each independently represent a methine or a nitrogen atom;
XB represents an oxygen atom, a sulfur atom, methylene or imino;
* Represents the position of bonding to the L ^{1 to} L ³ side in the general formula (IV);
** represents a position bonded to the R ^{1 to} R ³ side in the general formula (IV).

In general formula (IV), R < ¹ >, R < ² > and R < ³ > represent the following general formula (IV-R) each independently.

General formula (IV-R)
*-(-L ²¹ -Q ² ) _n1 -L ²² -L ²³ -Q ¹
In the general formula (IV-R), * represents a position bonded to the H ^{1 to} H ³ side in the general formula (IV).
L ²¹ represents a single bond or a divalent linking group. When L ²¹ is a divalent linking group, the group consisting of —O—, —S—, —C (═O) —, —NR ⁷ —, —CH═CH—, —C≡C—, and combinations thereof It is preferably a divalent linking group selected more. R ⁷ is an alkyl group having 1 to ⁷ carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group, an ethyl group or a hydrogen atom. Preferably, it is a hydrogen atom.

L ²¹ is a single bond, ***-O-CO-, ***-CO-O-, ***-CH = CH- and ***-C≡C- (where *** is general Any one of the formulas (DI-R) is preferred, and a single bond is more preferred.

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

Of Q ^2, the cyclic group having a benzene ring is preferably a 1,4-phenylene group. As the cyclic group having a naphthalene ring, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6 -A diylnaphthalene-2,7-diyl group is preferred. The cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. Among these, a 1,4-phenylene group, a naphthalene-2,6-diyl group, and a 1,4-cyclohexylene group are particularly preferable.

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

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

L ²² is **-O-, **-O-CO-, **-CO-O-, **-O-CO-O-, **-S-, **-NH-, ** —SO ₂ —, ** — CH ₂ —, ** — CH═CH—, or ** — C≡C— is represented, and ** represents a position bonded to the Q ² side.
L ²² is preferably ** — O—, ** — O—CO—, ** — CO—O—, ** — O—CO—O—, ** — CH ₂ —, ** — CH. ═CH—, ** — C≡C—, more preferably ** — O—, ** — O—CO—, ** — O—CO—O—, ** — CH ₂ —. . When L ²² is a group containing a hydrogen atom, the hydrogen atom may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ²³ represents —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Represents a divalent linking group selected from the group consisting of Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred. By being substituted by these substituents, when preparing a liquid crystalline composition from the liquid crystalline compound of the present invention, the solubility in a solvent to be used can be improved.

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

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

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

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

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

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

  Among the compounds of the formula (IV), a compound represented by the following general formula (IV ′) is more preferable.

In the general formula (DIV), Y ¹¹ , Y ¹² and Y ¹³ each independently represent methine or a nitrogen atom, methine is preferred, and methine is preferably unsubstituted.

R ¹¹ , R ¹² and R ¹³ each independently represent the following general formula (IV′-A), the following general formula (IV′-B) or the following general formula (IV′-C). In order to reduce the wavelength dispersion of intrinsic birefringence, general formula (IV′-A) or general formula (IV′-C) is preferable, and general formula (IV′-A) is more preferable. R ¹¹ , R ¹² and R ¹³ are preferably R ¹¹ = R ¹² = R ¹³ .

In general formula (IV′-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each independently represents a methine or nitrogen atom.
At least one of A ¹¹ and A ¹² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
Of A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ , at least three of them are preferably methine, more preferably all methine. Furthermore, methine is preferably unsubstituted.
Examples of substituents when A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ or A ¹⁶ is methine include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups An alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, and 1 carbon atom -16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C16 alkoxycarbonyl group, carbamoyl group, An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ¹ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

In the general formula (IV′-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represents a methine or nitrogen atom.
At least one of A ²¹ and A ²² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
Of A ²³ , A ²⁴ , A ²⁵ and A ²⁶ , at least three of them are preferably methine, more preferably all methine.
Examples of substituents when A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ or A ²⁶ is methine include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups An alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, and 1 carbon atom -16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C16 alkoxycarbonyl group, carbamoyl group, An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ² represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

In general formula (IV′-C), A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ and A ³⁶ each independently represents a methine or nitrogen atom.
At least one of A ³¹ and A ³² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
At least three of A ³³ , A ³⁴ , A ³⁵ and A ³⁶ are preferably methine, more preferably methine.
When A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ or A ³⁶ is methine, the methine may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ³ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

L ^{11 in} the general formula (IV′-A), L ^{21 in} the general formula (IV′-B), and L ³¹ in the general formula (IV′-C) are each independently —O—, —C (═O) —, —O—CO—, —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C≡C— is represented. Preferably, —O—, —C (═O) —, —O—CO—, —CO—O—, —O—CO—O—, —CH ₂ —, —CH═CH—, —C≡C are preferable. —, More preferably —O—, —O—CO—, —CO—O—, —O—CO—O—, —C≡C—. In particular, L ¹¹ in the general formula (DI-A) that can be expected to have small intrinsic birefringence wavelength dispersibility is particularly preferably —O—, —CO—O—, —C≡C—, and among them, —CO— -O- is preferable because it can exhibit a discotic nematic phase at a higher temperature. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ^{12 in} the general formula (IV′-A), L ^{22 in} the general formula (IV′-B), and L ³² in the general formula (IV′-C) are each independently —O—, —S. A divalent linking group selected from the group consisting of —, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Represents. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and 1 carbon atom. -6 alkoxy group, C2-C6 acyl group, C1-C6 alkylthio group, C2-C6 acyloxy group, C2-C6 alkoxycarbonyl group, carbamoyl group, Preferred examples include a carbamoyl group substituted with an alkyl having 2 to 6 carbon atoms and an acylamino group having 2 to 6 carbon atoms, and a halogen atom, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms are more preferable. A halogen atom, a methyl group, and an ethyl group are preferable.

L ¹² , L ²² and L ³² are each independently selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. It is preferable to be selected.

L ¹² , L ²² and L ³² each independently preferably have 1 to 20 carbon atoms, and more preferably 2 to 14 carbon atoms. The number of carbon atoms is preferably 2 to 14, more preferably 1 to 16 —CH ₂ —, and still more preferably ₂ to 12 —CH ₂ —.

The number of carbon atoms constituting L ¹² , L ²² , and L ³² affects the phase transition temperature of the liquid crystal and the solubility of the compound in the solvent. Generally the more increased the number of carbon atoms, transition temperature of the discotic nematic phase from (N _D phase) to the isotropic liquid tends to decrease. Further, the solubility in a solvent generally tends to improve as the number of carbon atoms increases.

Q ^{11 in} the general formula (IV′-A), Q ^{21 in} the general formula (IV′-B), and Q ³¹ in the general formula (IV′-C) each independently represent a polymerizable group or a hydrogen atom. Represent. Q ¹¹ , Q ²¹ and Q ³¹ are preferably a polymerizable group. The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Hereinafter, examples of the polymerizable group are the same as described above, and preferable examples are also the same as described above.

  Specific examples of the compound represented by the general formula (IV) include the exemplified compounds described in [Chemical Formula 13] to [Chemical Formula 43] of [0052] of JP-A-2006-76992, and JP-A-2007-2220. The compound shown in [Chemical Formula 13] of [Chemical Formula 13] to [0063] of [0040] in Japanese Patent Publication No. Gazette. However, it is not limited to these compounds.

  The above compound can be synthesized by various methods, for example, by the method described in JP-A 2007-2220, [0064] to [0070].

The discotic liquid crystal compound, a liquid crystal phase, it is preferred to exhibit a columnar phase and a discotic nematic phase (N _D phase), among these liquid crystal phases, a discotic nematic phase having a good monodomain property (N _D phase) is preferred.

  Among the discotic liquid crystal compounds, those that cause the liquid crystal phase to appear in the range of 20 ° C to 300 ° C are preferable. More preferably, it is 40 degreeC-280 degreeC, More preferably, it is 60 degreeC-250 degreeC. Here, the expression of the liquid crystal phase at 20 ° C. to 300 ° C. also means that the liquid crystal temperature range extends over 20 ° C. (for example, 10 ° C. to 22 ° C.) or 300 ° C. (for example, 298 ° C. to 310 ° C.). Including. The same applies to 40 ° C to 280 ° C and 60 ° C to 250 ° C.

  Since the discotic liquid crystal represented by the general formula (IV) has a plurality of aromatic rings in the molecule, a strong intermolecular π-π mutual bond is formed between the pyridinium compound or the imidazolium compound described later. As a result, the tilt angle near the interface of the alignment film of the discotic liquid crystal is increased. In particular, the discotic liquid crystal represented by the general formula (IV ′) has a highly linear molecular structure in which the rotational degrees of freedom of the molecules are constrained because a plurality of aromatic rings are connected by a single bond. Therefore, a stronger intermolecular π-π interaction occurs between the pyridinium compound or the imidazolium compound, and the tilt angle in the vicinity of the alignment film interface of the discotic liquid crystal can be increased to realize a vertical alignment state.

When a rod-like liquid crystal compound is used, it is preferable to horizontally align the rod-like liquid crystal. In the present specification, “horizontal alignment” means that the child major axis of the rod-like liquid crystal is parallel to the layer surface. It is not required to be strictly parallel, and in this specification, it means an orientation with an inclination angle of less than 10 degrees with the horizontal plane. The inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.
In the composition, an additive for accelerating the horizontal alignment of liquid crystal may be added. Examples of the additive are described in JP-A-2009-222001 [0055] to [0063]. These compounds are included.

When using a discotic liquid crystal, it is preferable to vertically align the discotic liquid crystal. In the present specification, “vertical alignment” means that the disc surface and the layer surface of the discotic liquid crystal are vertical. It is not required to be strictly perpendicular, and in this specification, it means an orientation having an inclination angle of 70 degrees or more with a horizontal plane. The inclination angle is preferably 85 to 90 degrees, more preferably 87 to 90 degrees, further preferably 88 to 90 degrees, and most preferably 89 to 90 degrees.
In addition, it is preferable to add the additive which accelerates | stimulates the vertical alignment of a liquid crystal in the said composition, The example of this additive is as above-mentioned.

In the optically anisotropic layer in which the liquid crystalline compound is aligned, the tilt angle on one surface of the optically anisotropic layer (the angle formed by the physical target axis in the liquid crystalline compound and the interface of the optically anisotropic layer) It is difficult to directly and accurately measure the tilt angle 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 a layer containing a liquid crystalline compound. Further, the minimum unit layer (assuming that the tilt angle of the liquid crystal compound is uniform in the layer) is assumed to be 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 the 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 measurements include KOBRA-21ADH and KOBRA-WR (manufactured by Oji Scientific Instruments), transmission 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 in each layer is no, the refractive index of extraordinary light is ne (ne is the same value in all layers, and no is the same), and the thickness of the entire multilayer body is d. And Further, based on the assumption that the tilt direction of each layer and the uniaxial optical axis direction of the layer coincide with each other, the calculation of the angular dependence of the retardation value of the optically anisotropic layer agrees with the measured value. Fitting is performed using the tilt angle θ1 on one surface of the isotropic layer and the tilt angle θ2 on the other surface as variables, and θ1 and θ2 are calculated.
Here, known values such as literature values and catalog values can be used for no and ne. If the value is unknown, it can also be measured using an Abbe refractometer. The thickness of the optically anisotropic layer can be measured by an optical interference film thickness meter, a cross-sectional photograph of a scanning electron microscope, or the like.

[Onium salt compound (alignment control agent on alignment film)]
In the present invention, as described above, an onium salt is preferably added in order to realize vertical alignment of a liquid crystal compound having a polymerizable group, particularly a discotic liquid crystal having a polymerizable group. The onium salt is unevenly distributed at the alignment film interface and acts to increase the tilt angle of the liquid crystal molecules in the vicinity of the alignment film interface.

As the onium salt, a compound represented by the following general formula (1) is preferable.
General formula (1)
Z- (YL-) _n Cy ⁺ .X-
In the formula, Cy represents a 5- or 6-membered onium group, and L, Y, Z, and X represent L ²³ , L ²⁴ , Y ²² , Y ²³ , Z ²¹ , and X in the general formula (II) described later. It is synonymous, the preferable range is also the same, and n represents an integer of 2 or more.

  The 5- or 6-membered onium group (Cy) is preferably a pyrazolium ring, an imidazolium ring, a triazolium ring, a tetrazolium ring, a pyridinium ring, a pyrazinium ring, a pyrimidinium ring, or a triazinium ring, and particularly preferably an imidazolium ring or a pyridinium ring.

The 5- or 6-membered onium group (Cy) preferably has a group having an affinity for the alignment film material. The onium salt compound has a high affinity with the alignment film material at the portion where the acid generator is not decomposed (unexposed portion) and is unevenly distributed at the alignment film interface. On the other hand, in the portion where the acid generator is decomposed and an acidic compound is generated (exposed portion), the anion of the onium salt is ion-exchanged, the affinity is lowered, and the uneven distribution at the alignment film interface is lowered. Since the hydrogen bond can be in a bonded state or in a state where the bond has disappeared within the actual temperature range for aligning the liquid crystal (room temperature to about 150 ° C.), it is preferable to use the affinity due to the hydrogen bond. . However, it is not limited to this example.
For example, in an embodiment in which polyvinyl alcohol is used as the alignment film material, it preferably has a hydrogen bonding group in order to form a hydrogen bond with the hydroxyl group of polyvinyl alcohol. As a theoretical interpretation of hydrogen bonding, for example, H.H. Unneyama and K.M. There are reports in Morokuma, Journal of American Chemical Society, Vol. 99, pp. 1316-1332, 1977. Specific examples of hydrogen bonding include J.I. N. Examples include Israes Ativiri, Yasuo Kondo, Hiroyuki Oshima, Intermolecular Force and Surface Force, McGraw Hill, 1991, page 98, FIG. Specific examples of hydrogen bonding include, for example, G.I. R. Examples include those described in Desiraju, Angelewan Chemistry International Edition England, Vol. 34, page 2311, 1995.

In addition to the hydrophilic effect of the onium group, the 5- or 6-membered onium group having a hydrogen bonding group enhances the surface unevenness of the alignment film interface by hydrogen bonding to the polyvinyl alcohol, and the polyvinyl alcohol main chain Promotes the function of imparting orthogonal orientation to the. Preferred hydrogen-bonding groups include amino groups, carbonamido groups, sulfonamido groups, acid amide groups, ureido groups, carbamoyl groups, carboxyl groups, sulfo groups, nitrogen-containing heterocyclic groups (for example, imidazolyl groups, benzimidazolyl groups, Pyrazolyl group, pyridyl group, 1,3,5-triazyl group, pyrimidyl group, pyridazyl group, quinolyl group, benzimidazolyl group, benzthiazolyl group, succinimide group, phthalimide group, maleimide group, uracil group, thiouracil group, barbituric acid group And hydantoin group, maleic hydrazide group, isatin group, uramil group and the like. More preferred hydrogen bonding groups include amino groups and pyridyl groups.
For example, it is also preferable that a 5- or 6-membered onium ring contains an atom having a hydrogen bonding group, such as a nitrogen atom of an imidazolium ring.

  n is preferably an integer of 2 to 5, more preferably 3 or 4, and particularly preferably 3. A plurality of L and Y may be the same as or different from each other. When n is 3 or more, the onium salt represented by the general formula (1) has three or more 5- or 6-membered rings, so that the discotic liquid crystal has a strong intermolecular π-π interaction. Therefore, the vertical alignment of the discotic liquid crystal, particularly the orthogonal vertical alignment with respect to the polyvinyl alcohol main chain can be realized on the polyvinyl alcohol alignment film.

The onium salt represented by the general formula (1) is particularly preferably a pyridinium compound represented by the following general formula (2a) or an imidazolium compound represented by the following general formula (2b).
The compounds represented by the general formulas (2a) and (2b) are added mainly for the purpose of controlling the alignment at the alignment film interface of the discotic liquid crystal represented by the general formulas (I) to (IV). In addition, there is an effect of increasing the tilt angle in the vicinity of the alignment film interface of the molecules of the discotic liquid crystal.

In the formula, L ²³ and L ²⁴ each represent a divalent linking group.
L ²³ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═CH—, —N═. N-, -O-AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O- CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO-AL-CO-O-. And AL is an alkylene group having 1 to 10 carbon atoms. L ²³ represents a single bond, —O—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, — CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO- AL-CO-O- is preferable, a single bond or -O- is more preferable, and -O- is most preferable.

L ²⁴ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═CH— or —N═. N- is preferred, and -O-CO- or -CO-O- is more preferred. When m is 2 or more, it is more preferred that the plurality of L ²⁴ are alternately —O—CO— and —CO—O—.

R ²² is a hydrogen atom, an unsubstituted amino group, or a substituted amino group having 1 to 20 carbon atoms.
When R ²² is a dialkyl-substituted amino group, two alkyl groups may be bonded to each other to form a nitrogen-containing heterocycle. The nitrogen-containing heterocycle formed at this time is preferably a 5-membered ring or a 6-membered ring. R ²³ is more preferably a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted amino group having 2 to 12 carbon atoms, and a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted group having 2 to 8 carbon atoms. Even more preferred is an amino group. When R ²³ is an unsubstituted amino group or a substituted amino group, the 4-position of the pyridinium ring is preferably substituted.

X is an anion.
X is preferably a monovalent anion. Examples of anions include halide ions (fluorine ions, chlorine ions, bromine ions, iodine ions) and sulfonate ions (eg, methanesulfonate ions, p-toluenesulfonate ions, benzenesulfonate ions).

Y ²² and Y ²³ are each a divalent linking group having a 5- or 6-membered ring as a partial structure.
The 5- or 6-membered ring may have a substituent. Preferably, at least one of Y ²² and Y ²³ is a divalent linking group having a 5- or 6-membered ring having a substituent as a partial structure. Y ²² and Y ²³ are preferably each independently a divalent linking group having a 6-membered ring which may have a substituent as a partial structure. The 6-membered ring includes an aliphatic ring, an aromatic ring (benzene ring) and a heterocyclic ring. Examples of the 6-membered aliphatic ring include a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring. Examples of 6-membered heterocycles include pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. Including. Another 6-membered ring or 5-membered ring may be condensed to the 6-membered ring.
Examples of the substituent include a halogen atom, cyano, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. The alkyl group and the alkoxy group may be substituted with an acyl group having 2 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms. The substituent is preferably an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms. The number of substituents may be 2 or more. For example, when Y ²² and Y ²³ are phenylene groups, the number of carbon atoms of 1 to 4 is 1 to 12 (more preferably 1 to 6, more preferably 1 to 6). The alkyl group of 3) may be substituted.

Here, m is 1 or 2, and is preferably 2. When m is 2, the plurality of Y ²³ and L ²⁴ may be the same as or different from each other.

Z ²¹ is halogen-substituted phenyl, nitro-substituted phenyl, cyano-substituted phenyl, phenyl substituted with an alkyl group having 1 to 10 carbon atoms, phenyl substituted with an alkoxy group having 2 to 10 carbon atoms, carbon atom An alkyl group having 1 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and 7 to 26 carbon atoms And a monovalent group selected from the group consisting of an arylcarbonyloxy group having 7 to 26 carbon atoms.
When m is 2, Z ²¹ is preferably cyano, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and is an alkoxy group having 4 to 10 carbon atoms. Is more preferable.
When m is 1, Z ²¹ is an alkyl group having 7 to 12 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an acyl-substituted alkyl group having 7 to 12 carbon atoms, or 7 carbon atoms. It is preferably an acyl-substituted alkoxy group of -12, an acyloxy-substituted alkyl group having 7-12 carbon atoms, or an acyloxy-substituted alkoxy group having 7-12 carbon atoms.

  The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.

p is an integer of 1-10. It is particularly preferable that p is 1 or 2. C _p H _2p means a chain alkylene group which may have a branched structure. C _p H _2p is preferably a linear alkylene group (— (CH ₂ ) _p —).

In the formula (2b), R ³⁰ is a hydrogen atom or an alkyl group having 1 to 12 (more preferably 1 to 6, more preferably 1 to 3) carbon atoms.

  Among the compounds represented by the formula (2a) or (2b), a compound represented by the following formula (2a ′) or (2b ′) is preferable.

In the formulas (2a ′) and (2b ′), the same symbols as those in the formula (2) have the same meaning, and the preferred ranges are also the same. L ²⁵ has the same meaning as L ²⁴ , and the preferred range is also the same. L ²⁴ and L ²⁵ are preferably —O—CO— or —CO—O—, L ²⁴ is preferably —O—CO—, and L ²⁵ is preferably —CO—O—.

R ²³ , R ²⁴ and R ²⁵ are each an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6, more preferably 1 to 3). n ₂₃ is 0-4, n ₂₄ is 1 to 4, and n ₂₅ represents 0 to 4. In n ₂₃ and n ₂₅ is 0, n ₂₄ is preferably a 1-4 (more preferably 1-3).
R ³⁰ is preferably an alkyl group having 1 to 12 carbon atoms (more preferably 1 to 6, more preferably 1 to 3).

  Specific examples of the compound represented by the general formula (1) include compounds described in [0058] to [0061] in JP-A-2006-113500.

Specific examples of the compound represented by the general formula (1) are shown below. However, the anion (X ⁻ ) was omitted in the following formula.

The compounds of the formulas (2a) and (2b) can be produced by a general method. For example, the pyridinium derivative of the formula (2a) is generally obtained by alkylating the pyridine ring (Menstokin reaction).
The addition amount of the onium salt does not exceed 5% by mass with respect to the liquid crystal compound, and is preferably about 0.1 to 2% by mass.

The onium salts represented by the general formulas (2a) and (2b) are unevenly distributed on the hydrophilic polyvinyl alcohol alignment film surface because the pyridinium group or the imidazolium group is hydrophilic. In particular, a pyridinium group is further substituted with an amino group which is a substituent of an acceptor of a hydrogen atom (in the general formulas (2a) and (2a ′), R ²² is an unsubstituted amino group or a carbon atom having 1 to 20 carbon atoms) When the amino group is substituted, intermolecular hydrogen bonds are generated with the polyvinyl alcohol, and it is unevenly distributed on the surface of the alignment film at a higher density, and due to the effect of the hydrogen bonds, the pyridinium derivative is a main chain of the polyvinyl alcohol. Alignment in a direction orthogonal to the direction of the liquid crystal promotes the orthogonal alignment of the liquid crystal with respect to the rubbing direction. Since the pyridinium derivative has a plurality of aromatic rings in the molecule, a strong intermolecular π-π interaction occurs between the liquid crystal, particularly the discotic liquid crystal, and the alignment film of the discotic liquid crystal. Induces orthogonal orientation near the interface. In particular, as represented by the general formula (2a ′), when a hydrophobic aromatic ring is connected to a hydrophilic pyridinium group, it also has an effect of inducing vertical alignment due to the hydrophobic effect.

  The onium salt has a property of being unevenly distributed at the interface of the alignment film made of polyvinyl alcohol or the like. When the onium salt is unevenly distributed at the alignment film interface, the liquid crystal (especially discotic liquid crystal) tends to be vertically aligned (hereinafter referred to as “orthogonal vertical alignment”) with its slow axis perpendicular to the rubbing direction. There is. On the other hand, in a state where the onium salt is not unevenly distributed at the alignment film interface, the liquid crystal (particularly the discotic liquid crystal) is aligned according to the alignment control ability of the original rubbing alignment film, that is, its slow axis is parallel to the rubbing direction. Tends to be vertically aligned (hereinafter referred to as parallel vertical alignment). If the onium salt alignment film interface uneven distribution property can be turned on and off, a region in which the liquid crystals are orthogonally vertically aligned and a region in which the liquid crystal is horizontally aligned can be formed in a pattern. ON / OFF of the onium salt alignment film interface uneven distribution property can be controlled by an acidic compound generated by a photoacid generator contained in the alignment film or by external stimulation such as heating.

[Fluoroaliphatic group-containing copolymer (air interface orientation control agent)]
The fluoroaliphatic group-containing copolymer is added for the purpose of controlling the orientation of the liquid crystal at the air interface, and has the effect of increasing the tilt angle near the air interface of the liquid crystal molecules. Furthermore, applicability such as unevenness and repellency is also improved.
Examples of the fluoroaliphatic group-containing copolymer that can be used in the present invention include JP-A Nos. 2004-333852, 2004-333863, 2005-134484, 2005-179636, and 2005-181977. It can be used by selecting from the compounds described in each publication and specification. Particularly preferably, a fluoroaliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy described in JP-A Nos. 2005-179636 and 2005-181977 and the specification thereof. {-OP (= O) (OH) ₂ }} and a polymer containing one or more hydrophilic groups selected from the group consisting of salts thereof in the side chain.
The addition amount of the fluoroaliphatic group-containing copolymer does not exceed 2% by mass relative to the liquid crystal compound, and is preferably about 0.1 to 1% by mass.

The fluoroaliphatic group-containing copolymer increases the uneven distribution at the air interface due to the hydrophobic effect of the fluoroaliphatic group, and provides a low surface energy field on the air interface side, and tilts liquid crystals, particularly discotic liquid crystals. The corner can be increased. And one or more hydrophilic groups selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy {—OP (═O) (OH) ₂ }} and salts thereof; In the side chain, a vertical alignment of the liquid crystal compound can be realized by charge repulsion between these anions and π electrons of the liquid crystal.

[Polymerization initiator]
A composition containing a liquid crystal compound having a polymerizable group (for example, a coating solution) is brought into an alignment state exhibiting a desired liquid crystal phase, and then the polymerization reaction proceeds to fix the alignment state (of the above method). 5) Step). The immobilization is preferably performed by a polymerization reaction of a reactive group introduced into the liquid crystal compound. It is preferable to fix by a photopolymerization reaction by ultraviolet irradiation. The photopolymerization reaction may be either radical polymerization or cationic polymerization. Examples of radical photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Aciloin 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, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970). Examples of the cationic photopolymerization initiator include organic sulfonium salt systems, iodonium salt systems, phosphonium salt systems, and the like. Organic sulfonium salt systems are preferable, and triphenylsulfonium salts are particularly preferable. As counter ions of these compounds, hexafluoroantimonate, hexafluorophosphate, and the like are preferably used.
The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution.

[Sensitizer]
In addition to a polymerization initiator, a sensitizer may be used for the purpose of increasing sensitivity. Examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, thioxanthone and the like. Multiple photopolymerization initiators may be combined, and the amount used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. The light irradiation for the polymerization of the liquid crystal compound preferably uses ultraviolet rays.

[Other additives]
Apart from the polymerizable liquid crystal compound, the composition may contain a non-liquid crystalline polymerizable monomer. As the polymerizable monomer, a compound having a vinyl group, a vinyloxy group, an acryloyl group or a methacryloyl group is preferable. Note that it is preferable to use a polyfunctional monomer having two or more polymerizable reactive functional groups, for example, ethylene oxide-modified trimethylolpropane acrylate because durability is improved. Since the non-liquid crystalline polymerizable monomer is a non-liquid crystalline component, the addition amount thereof does not exceed 40 mass% with respect to the liquid crystal compound, and is preferably about 0 to 20 mass%.

  The thickness of the pattern / letter layer is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

Alignment film:
In the method of the present invention, it is preferable to use an alignment film for forming the patterned retarder layer. Examples of alignment films that can be used include rubbing alignment films and photo-alignment films. The “rubbing alignment film” means a film that has been processed by rubbing so as to have alignment ability of liquid crystal molecules. The rubbing alignment film has an alignment axis that regulates alignment of liquid crystal molecules, and the liquid crystal molecules are aligned according to the alignment axis. In the present invention, the liquid crystal molecules are aligned so that the slow axis of the liquid crystal is parallel to the rubbing direction in the ultraviolet irradiation portion of the alignment film, and the slow axis of the liquid crystal molecules is in the rubbing direction in the unirradiated portion. It is preferable to use a pattern rubbing alignment film that is orthogonally aligned. The pattern rubbing alignment film can be formed by using a photoacid generator. Further, a pattern rubbing alignment film may be formed by mask rubbing.

  The rubbing alignment film generally contains a polymer as a main component. The polymer material for alignment film is described in many documents, and many commercially available products can be obtained. The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred. Polyvinyl alcohols having various saponification degrees exist. In the present invention, those having a saponification degree of about 85 to 99 are preferably used. Commercial products may be used. For example, “PVA103”, “PVA203” (manufactured by Kuraray Co., Ltd.) and the like are PVA having the above saponification degree. For the rubbing alignment film, reference can be made to the modified polyvinyl alcohol described in WO01 / 88574A1, page 43, line 24 to page 49, line 8, and paragraph Nos. [0071] to [0095] of Japanese Patent No. 3907735. The thickness of the rubbing alignment film is preferably from 0.01 to 10 μm, and more preferably from 0.01 to 1 μm.

The rubbing treatment can be generally performed by rubbing the surface of a film containing a polymer as a main component several times in a certain direction with paper or cloth. A general method of rubbing is described in, for example, “Liquid Crystal Handbook” (issued by Maruzen, October 30, 2000).
As a method for changing the rubbing density, a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used. The rubbing density (L) is quantified by the following formula (A).
Formula (A) L = Nl (1 + 2πrn / 60v)
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed).

In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can reverse this.
Between the rubbing density and the pretilt angle of the alignment film, there is a relationship in which the pretilt angle decreases as the rubbing density increases and the pretilt angle increases as the rubbing density decreases.
In order to bond a long polarizing film with an absorption axis in the longitudinal direction, an alignment film is formed on a support made of a long polymer film, and the direction is 45 ° to the longitudinal direction. It is preferable to perform a rubbing treatment continuously to form a rubbing alignment film.

Photoacid generator:
An example of the pattern rubbing alignment film used in the present invention contains at least one photoacid generator. The photoacid generator is a compound that decomposes upon irradiation with light such as ultraviolet rays to generate an acidic compound. When the photoacid generator is decomposed by light irradiation to generate an acidic compound, the alignment control ability of the alignment film changes. The change in the alignment control ability here is included in the alignment film and the composition for forming an optically anisotropic layer disposed on the alignment film, even if it is specified as a change in the alignment control ability of the alignment film alone. It may be specified as a change in the orientation control ability achieved by the additive or the like, or may be specified as a combination thereof.
A discotic (discotic) liquid crystal to be described later may be in an orthogonal vertical alignment state by adding an onium salt. When the acid generated by decomposition and the onium salt are anion-exchanged, the uneven distribution at the interface of the alignment film of the onium salt may be reduced, the orthogonal vertical alignment effect may be reduced, and a parallel vertical alignment state may be formed. Further, for example, when the alignment film is a polyvinyl alcohol-based alignment film, the ester portion may be decomposed by the generated acid, and as a result, the alignment film interface uneven distribution of the onium salt may be changed.

As the photoacid generator used for the alignment film, a water-soluble compound is preferably used. Examples of photoacid generators that can be used include Prog. Polym. Sci. , 23, 1485 (1998).
As the photoacid generator, pyridinium salts, iodonium salts and sulfonium salts are particularly preferably used. Preferable examples of the pyridinium salt, iodonium salt, and sulfonium salt include salts represented by the following general formulas.

In the formula, each R is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Or a halogen atom. Y is a straight-chain alkyl group or branched alkyl group having 1 to 6 carbon atoms, a straight-chain alkoxy group or branched alkoxy group having 1 to 6 carbon atoms. X- represents a counter anion of a pyridinium salt, an iodonium salt or a sulfonium salt, and becomes an anion of an acidic compound generated by decomposition. PF ₆ ⁻ , BF ₄ ⁻ , or C _n F _{2n + 1} SO ₃ ⁻ (where n is an integer of 1 to 12) is preferable. For example, X- is BF ₄ ^- from a is a photoacid generator, the acid HBF ₄ is generated by the decomposition, X- is PF ₆ ^- from a is a photoacid generator, HPF ₆ occurs, X- is _{C n F 2n + 1 SO 3} - from a is a photoacid _{generator, C n F 2n + 1 SO} 3 H is generated.

  Although the specific example of the photo-acid generator which can be utilized for this invention below is shown, it is not limited to these. In the following specific examples, a salt in which an anion is specified is illustrated, but a specific example in which the anion is replaced with another anion is also illustrated as a specific example of a usable photoacid generator.

  The composition used for forming the alignment film is preferably prepared as a coating solution. The solvent used for the preparation of the coating preferably contains water, more preferably contains 20% by mass or more, more preferably 50-80% by mass of water. By using a coating solution prepared with a water-containing solvent, elution of the support by the solvent can be suppressed or controlled when coating on the support.

  The content of each component in the alignment film composition can be appropriately set so that a stable alignment film can be formed. For example, the content of the alignment layer polymer material as the main component is 2.0 to 10.0 mass%, preferably 2.0 to 5.0 mass%, based on the total amount of the composition (including the solvent). It can be. The addition amount of the photoacid generator can be appropriately set within a range in which ion exchange with the counter anion of the onium salt described above can be performed, for example, 0.1 to 10.0% by mass with respect to the polymer material for alignment film, Preferably it can be 0.5-5.0 mass%. Moreover, the solvent amount in a composition can be 80-98 mass% with respect to the total amount of a composition, for example, Preferably it can be 90-97 mass%.

  In the present invention, a photo-alignment film may be used. As a photo-alignment material used for forming a photo-alignment film, there are many literatures. In the present invention, for example, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007-. 140465, JP 2007-156439 A, JP 2007-133184 A, JP 2009-109831 A, JP 3888848 A, JP 4151746 A4, and JP 2002-229039 A2. An aromatic ester compound described in JP-A-2002-265541, JP-A-2002-317013, a maleimide and / or alkenyl-substituted nadiimide compound having a photo-alignment unit, Japanese Patent No. 4205195, Japanese Patent No. 4205198 Photocrosslinkable silane derivatives as described in Body, Kohyo 2003-520878, JP-T-2004-529220, JP-photocrosslinkable polyimides described in Japanese Patent No. 4162850, polyamide, or an ester are preferred examples. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.

2. Film / Pattern Retarder and Use Thereof One aspect of the film / patterned retarder produced by the method of the present invention is shown in FIG. 1 as a schematic cross-sectional view. It has a layer 12. As shown in a top view in FIG. 2, the optically anisotropic layer 12 is a patterned retarder layer in which the first and second retardation regions 12a and 12b are arranged equally and symmetrically. The first and second retardation regions 12a and 12b have in-plane slow axes a and b that are orthogonal to each other. In the embodiment using circularly polarized light, the Re of the first and second optical films 10 is preferably λ / 4, specifically 110 to 165 nm. Re is particularly preferably 120 to 145 nm. When the film 16 is a retardation film, it is preferable that Re as a whole of the film / patterned retarder including Re of the film 16 is in the above range. In one example, the film 16 is made of a low-Re film, and specifically, Re (550) of the film 16 is 0 to 10 nm. On the other hand, the smaller Rth as a whole, the better from the viewpoint of reducing crosstalk. Specifically, the absolute value of Rth as a whole is preferably 20 nm or less.

  The alignment film 14 may be a pattern alignment film. One embodiment of the alignment film 14 contains at least a photoacid generator together with a main component polymer such as polyvinyl alcohol or modified polyvinyl alcohol, the surface of which is aligned in one direction, and the degree of decomposition of the photoacid generator Includes first and second alignment control regions different from each other, and the first and second alignment control regions are pattern alignment films alternately arranged in a plane. The degree of decomposition of the photoacid generator can be determined by quantifying the content of the acidic compound produced by the decomposition of the photoacid generator in each orientation control region. One aspect of the alignment film used for the patterned optical anisotropic layer having the first and second retardation regions 12a and 12b is the first and second retardation regions 12a and 12b corresponding to the first and second retardation regions 12a and 12b, respectively. A pattern alignment film having a second alignment control region, wherein the photoacid generators in the first and second alignment control regions have different degrees of decomposition, that is, in the first and second alignment control regions, respectively. It is a pattern alignment film in which the ratios of acidic compounds generated by decomposition of the contained photoacid generator are different from each other. In the patterned alignment film of this embodiment, there is a difference in alignment control ability depending on the concentration of the acidic compound generated by the decomposition of the photoacid generator contained in each of the first and second alignment control regions, or the concentration of ions constituting the compound. Is provided. In one example of the pattern alignment film of this aspect, one of the first and second alignment control regions contains the photoacid generator undecomposed, and the other proceeds with decomposition of the photoacid generator, thereby It is an alignment film containing the generated acidic compound.

  Although the alignment film 14 preferably has first and second alignment control regions having different alignment control capabilities, it is not necessary to perform alignment processing for expressing the alignment regulating force in a plurality of directions. That is, it is not necessary to perform complicated alignment processing such as mask rubbing for rubbing in different directions. It is preferable to perform orientation treatment in one direction. For example, as shown in FIG. 3, one mode of the alignment film used for the patterned optical anisotropic layer having the first and second retardation regions 12a and 12b is an in-plane retardation of the first retardation region 12a. The alignment film is rubbed in the C1 or C2 direction that coincides with the in-plane slow axis b of the phase axis a or the second retardation region 12b.

  When the film / patterned retarder shown in FIGS. 1 and 2 is combined with a linear polarizing film, the in-plane slow axes a and b of the first and second retardation regions 12a and 12b are respectively set as shown in FIG. The linearly polarizing film 18 is disposed so as to be ± 45 ° with respect to the transmission axis P. With this configuration, it is possible to separate right-eye and left-eye circularly polarized images. Further, the viewing angle may be further increased by further laminating λ / 2 plates.

  The film patterned retarder produced by the method of the present invention is not limited to the layer structure shown in FIG. For example, it is preferable to have an antireflection layer on the outer side of the patterned retarder layer, since the display characteristics can be improved when it is arranged on the outer side of the image display device. The antireflection layer may be bonded to the film / patterned retarder while being supported by the base film. There is no restriction | limiting in particular as a base film, For example, the film similar to the film for supports of a patterned retarder layer can be used.

  The antireflection layer is not particularly limited. An antireflection layer in which a light scattering layer and a low refractive index layer are laminated in this order, or an antireflection layer in which a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order, and the like are preferably used. This is because flickering due to external light reflection can be effectively prevented, particularly when displaying a stereoscopic image. The antireflection layer may further include a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like. Details of each layer constituting the antireflection layer are described in [0182] to [0220] of JP-A-2007-254699, and preferable characteristics, preferable materials, and the like for the antireflection layer that can be used in the present invention. The same applies to.

  FIG. 5 is a schematic cross-sectional view of several examples of film patterned retarders manufactured by the method of the present invention, each having an antireflection layer, in combination with a liquid crystal display panel unit. However, these are not limited. In FIG. 5, the configuration of the liquid crystal panel is shown as the display panel unit. However, the configuration is not limited to the liquid crystal panel, and various display panel configurations such as an organic EL display panel and a plasma display panel can be used. it can.

The film patterned retarder produced by the method of the present invention can be used for an image display device and a stereoscopic image display system. An example of the image display device is:
First and second polarizing films;
A liquid crystal cell, which is disposed between the first and second polarizing films, and includes a pair of substrates having electrodes disposed on at least one side thereof and facing each other; and a liquid crystal layer between the pair of substrates; and the first polarizing film An image display device having at least the film-patterned retarder on the outside thereof,
The image display device is characterized in that the absorption axis direction of the first polarizing film and the in-plane slow axes of the first and second retardation regions of the patterned retarder layer form an angle of ± 45 °, respectively. .
An example of the stereoscopic image display system includes at least the image display device and a third polarizing plate disposed outside the film-patterned retarder, and visually recognizes a stereoscopic image through the third polarizing plate. This is a stereoscopic image display system.

  The image display devices include TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroelectric Liquid Crystal), OCB (Optic LiquidTypical). Any display mode such as VA (Vertically Aligned) and HAN (Hybrid Aligned Nematic) may be used.

Third polarizing plate:
In the stereoscopic image display system, an image is recognized through a spectacle-shaped polarizing plate (third polarizing plate) in order to make the viewer recognize a stereoscopic image called a 3D image.
[Polarized glasses]
The video display system includes polarized glasses in which slow axes of right glasses and left glasses are orthogonal to each other, and image light for the right eye emitted from one of the first and second phase difference regions of the optical film. Passes through the right glasses and is shielded by the left glasses; the image light for the left eye emitted from the other of the first and second phase difference regions is transmitted through the left glasses and shielded by the right glasses It is preferable that it is comprised.
The polarizing glasses form polarizing glasses by including a retardation functional layer and a linear polarizer. In addition, you may use the other member which has a function equivalent to a linear polarizer.

  A specific configuration of the video display system including polarized glasses will be described. First, the film-patterned retarder is formed on a plurality of first lines and a plurality of second lines that are alternately repeated on the video display panel (for example, on odd-numbered lines in the horizontal direction if the lines are in the horizontal direction). The first phase difference region and the second phase difference region having different polarization conversion functions are provided on the even number line and may be on the odd number odd line and the even number line if the line is vertical. It has been. When circularly polarized light is used for display, the phase difference between the first phase difference region and the second phase difference region is preferably λ / 4, and the first phase difference region is More preferably, the slow axis of the second phase difference region is orthogonal.

When using circularly polarized light, the phase difference values of the first phase difference region and the second phase difference region are both set to λ / 4, an image for the right eye is displayed on the odd line of the video display panel, and the odd line If the slow axis of the phase difference region is 45 degrees, it is preferable to arrange λ / 4 plates on both the right and left glasses of the polarized glasses, and the slow phase of the λ / 4 plates of the right glasses of the polarized glasses. Specifically, the shaft may be fixed at approximately 45 degrees. In the above situation, similarly, the left eye image is displayed on the even line of the video display panel, and if the slow axis of the even line phase difference region is in the direction of 135 degrees, the left eyeglass of the polarizing glasses Specifically, the slow axis may be fixed at approximately 135 degrees.
Furthermore, from the viewpoint of emitting image light as circularly polarized light once in the film-patterned retarder and returning the polarization state to the original by the polarized glasses, the angle of the slow axis fixed by the right glasses in the above example is The closer to 45 degrees in the horizontal direction, the better. Further, it is preferable that the angle of the slow axis fixed by the left spectacles is exactly close to horizontal 135 degrees (or -45 degrees).

For example, when the video display panel is a liquid crystal display panel, the absorption axis direction of the front-side polarizing plate of the liquid crystal display panel is usually a horizontal direction, and the absorption axis of the linear polarizer of the polarizing glasses is the front-side polarization The direction perpendicular to the absorption axis direction of the plate is preferable, and the absorption axis of the linear polarizer of the polarizing glasses is more preferably the vertical direction.
In addition, the absorption axis direction of the front-side polarizing plate of the liquid crystal display panel and the slow axes of the odd-numbered and even-numbered line retardation regions of the film-patterned retarder are 45 in terms of the efficiency of polarization conversion. It is preferable to make a degree.
A preferable arrangement of such polarized glasses, the film patterned retarder, and the liquid crystal display device is disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-170693.

  Examples of polarized glasses include those described in Japanese Patent Application Laid-Open No. 2004-170693, and examples of commercially available products include accessories of ZM-man and ZM-M220W.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

Example 1
<Preparation of transparent support A>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acylate solution A.
────────────────────────────────────
Composition of Cellulose Acylate Solution A────────────────────────────────────
Cellulose acetate having a substitution degree of 2.86 100 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) ) 54 parts by mass 1-butanol 11 parts by mass ─────────────────────────────────────

The following composition was charged into another mixing tank, stirred while heating to dissolve each component, and an additive solution B was prepared.
────────────────────────────────────
Composition of additive solution B ─────────────────────────────────────
The following compound B1 (Re reducing agent) 40 parts by mass The following compound B2 (wavelength dispersion controlling agent) 4 parts by mass Methylene chloride (first solvent) 80 parts by mass Methanol (second solvent) 20 parts by mass ──────── ────────────────────────────

<< Preparation of transparent cellulose acetate support >>
A dope was prepared by adding 40 parts by mass of the additive solution B to 477 parts by mass of the cellulose acylate solution A and stirring sufficiently. The dope was cast from a casting port onto a drum cooled to 0 ° C. The film is peeled off at a solvent content of 70% by mass, and both ends in the width direction of the film are fixed with a pin tenter (a pin tenter described in FIG. 3 of JP-A-4-1009), and the solvent content is 3 to 5% by mass. Then, it was dried while maintaining an interval at which the stretching ratio in the transverse direction (direction perpendicular to the machine direction) was 3%. Then, it dried further by conveying between the rolls of a heat processing apparatus, and produced the 60-micrometer-thick cellulose acetate protective film (transparent support body A). Transparent support A did not contain an ultraviolet absorber, Re (550) was 0 nm, and Rth (550) was 12.3 nm.

<< Alkaline saponification treatment >>
The cellulose acetate transparent support A is passed through a dielectric heating roll having a temperature of 60 ° C., and the film surface temperature is raised to 40 ° C. Then, an alkali solution having the composition shown below is applied to one side of the film using a bar coater. The coating was applied at a coating amount of 14 ml / m ² , heated to 110 ° C., and conveyed for 10 seconds under a steam far infrared heater manufactured by Noritake Company Limited. Subsequently, 3 ml / m ^{2 of} pure water was applied using the same bar coater. Next, washing with a fountain coater and draining with an air knife were repeated three times, followed by transporting to a drying zone at 70 ° C. for 10 seconds and drying to prepare an alkali saponified cellulose acetate transparent support A. The Tg of the transparent support A was about 180 ° C.

───────────────────────────────────
Composition of alkaline solution (parts by mass)
───────────────────────────────────
Potassium hydroxide 4.7 parts by weight Water 15.8 parts by weight Isopropanol 63.7 parts by weight Surfactant SF-1: C ₁₄ H ₂₉ O (CH ₂ CH ₂ O) ₂₀ H 1.0 part by weight Propylene glycol 14. 8 parts by mass ───────────────────────────────────

<Preparation of transparent support with rubbing alignment film>
A rubbing alignment film coating solution having the following composition was continuously applied with a # 8 wire bar to the saponified surface of the prepared support. The alignment film was formed by drying with hot air of 60 ° C. for 60 seconds and further with hot air of 145 ° C. (= T ₁ ) (film surface temperature of 125 ° C. (= T _1S )) for 60 minutes. Next, a stripe mask (width of 1050 stripes: total pitch of 299.25 mm) having a lateral stripe width of 285 μm at the transmission part and a lateral stripe width of 285 μm at the shielding part is placed on the rubbing alignment film, and UV- First, ultraviolet rays were irradiated for 4 seconds using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) having an illuminance of 2.5 mW / cm ² in the C region to decompose the photoacid generator and generate an acidic compound. An alignment layer for retardation region was formed. Thereafter, a rubbing treatment was performed once in one direction at 500 rpm while maintaining an angle of 45 ° with respect to the stripe of the stripe mask, and a transparent support with a rubbing alignment film was produced. The alignment film had a thickness of 0.5 μm.
────────────────────────────────────
Composition of coating solution for alignment film formation ────────────────────────────────────
3.9 parts by mass of polymer material for alignment film (PVA103, Kuraray Co., Ltd. polyvinyl alcohol)
Photoacid generator (S-2) 0.1 parts by weight Methanol 36 parts by weight Water 60 parts by weight ──────────────────────────── ────────

<Preparation of patterned optically anisotropic layer A>
The following coating liquid for optically anisotropic layer was applied at a coating amount of 4 ml / m ² using a bar coater. Next, after aging for 2 minutes at a film surface temperature of 110 ° C., it was cooled to 80 ° C. and irradiated with ultraviolet rays for 20 seconds using an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) of 20 mW / cm ^{2 in} the air. Then, the patterned optical anisotropic layer A was formed by fixing the orientation state. In the mask exposure portion (first retardation region), the discotic liquid crystal is vertically aligned with the slow axis direction parallel to the rubbing direction, and the unexposed portion (second retardation region) is orthogonally aligned perpendicularly. It was. The film thickness of the optically anisotropic layer was 0.9 μm.

────────────────────────────────────
Composition of coating solution for optically anisotropic layer ────────────────────────────────────
Discotic liquid crystal E-1 100 parts by mass alignment film interface alignment agent (II-1) 3.0 parts by mass air interface alignment agent (P-1) 0.4 parts by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 400 parts by weight ───────────────────────── ───────────

The first retardation region and the second retardation region of the formed patterned optical anisotropic layer A are each analyzed by TOF-SIMS (time-of-flight secondary ion mass spectrometry, TOF-SIMS V manufactured by ION-TOF). As a result, in the first retardation region and the second retardation region, the abundance ratio of the photoacid generator S-2 in the corresponding alignment layer is 8 to 92, and in the first retardation region, S-2 is It was found that it was almost decomposed. Further, in the optically anisotropic layer, the anion BF ₄ ⁻ of the acid HBF ₄ generated from the cation of II-1 and the photoacid generator S-2 exists at the air interface in the first retardation region. Was confirmed. These ions were hardly observed at the air interface in the second retardation region, and it was found that II-1 cations and Br ⁻ were present in the vicinity of the alignment film interface. The abundance ratio of each ion at the air interface was 93: 7 for II-1 cations and 90:10 for BF ₄ ⁻ . From this, the alignment film interface aligning agent (II-1) is unevenly distributed at the alignment film interface in the second retardation region, but the uneven distribution is decreased in the first retardation region and diffused to the air interface. In the first retardation region, it can be understood that diffusion of the II-1 cation is promoted by anion exchange between the generated acid HBF ₄ and II-1.

Polarization of either one of the two polarizing plates in which the slow axis of one of the first retardation region and the second retardation region is combined in the orthogonal position with the patterned optically anisotropic layer A The optically anisotropic layer is placed between the polarizing plates so as to be parallel to the axis, and a sensitive color plate having a phase difference of 530 nm is formed so that the slow axis forms an angle of 45 ° with the polarizing axis of the polarizing plate. I was on top. Next, the state where the optically anisotropic layer was rotated by + 45 ° was observed. As is clear from this observation result, when rotated by + 45 °, the slow axis of the first retardation region and the slow axis of the sensitive color plate are parallel, so the phase difference is larger than 530 nm, The color has changed to blue (in the black-and-white drawing, the dark and light part). On the other hand, since the slow axis of the second phase difference region is orthogonal to the slow axis of the sensitive color plate, the phase difference is smaller than 530 nm, and the color changes to white (the light and shaded part in the black and white drawing). To do.
That is, as shown in FIG. 6, the optically anisotropic layer A in which the first and second retardation regions having in-plane slow axes of ± 45 ° with respect to the longitudinal direction of the stripe pattern are alternately arranged. It was confirmed that it was formed. As shown in FIG. 6, the pitch of the first and second phase difference regions is ideally 285 μm, which is equal to the pitch of the transmission part and the light shielding part of the mask.

(Evaluation of optically anisotropic layer)
The distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P ₁ was calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.19 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 60 μm. It was. The rate of change ΔP / P ₁ was 0.02%, which was small.
Further, from the results shown in the following table, after the discotic liquid crystal is mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, A patterned optically anisotropic layer having a first retardation region and a second retardation region which are perpendicularly aligned and whose slow axes are orthogonal to each other by being aligned on the alignment film rubbed in one direction Can also be obtained.

<Preparation of surface film A>
<< Preparation of antireflection film >>
[Preparation of coating liquid A for hard coat layer]
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution A.
To 900 parts by mass of methyl ethyl ketone, 100 parts by mass of cyclohexanone, 750 parts by mass of partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.), silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) ) 200 parts by mass and 50 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) 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.

[Preparation of coating liquid A for medium refractive index layer]
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (solid content), average particle size of zirconium oxide fine particles: about 20 nm, Solvent composition: methyl isobutyl ketone / methyl ethyl ketone = 9/1, manufactured by JSR Corporation]) 5.1 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1.5 parts by mass, light A polymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts by mass, methyl ethyl ketone 66.6 parts by mass, methyl isobutyl ketone 7.7 parts by mass and cyclohexanone 19.1 parts by mass were added and stirred. did. After sufficiently stirring, the mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution A for medium refractive index layer.

[Preparation of coating liquid B for medium refractive index layer]
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 4.5 parts by mass, photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) 0.14 parts by mass, methyl ethyl ketone 66.5 Part by mass, 9.5 parts by mass of methyl isobutyl ketone and 19.0 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, it was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution B for medium refractive index layer.

  A medium refractive index coating solution was prepared by mixing an appropriate amount of medium refractive index coating solution A and medium refractive index coating solution B so that the refractive index was 1.36 and the film thickness was 90 μm.

[Preparation of coating solution for high refractive index layer]
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (solid content), average particle size of zirconium oxide fine particles: about 20 nm, Photopolymerization initiator contained, solvent composition: methyl isobutyl ketone / methyl ethyl ketone = 9/1, manufactured by JSR Corporation]) 14.4 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 0 .75 parts by mass, 62.0 parts by mass of methyl ethyl ketone, 3.4 parts by mass of methyl isobutyl ketone, and 1.1 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the mixture was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution C for a high refractive index layer.

[Preparation of coating solution for low refractive index layer]
(Synthesis of perfluoroolefin copolymer (1))

Into an autoclave with a stirrer made of stainless steel having an internal volume of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.53 MPa (5.4 kg / cm ² ). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kg / cm ² ), the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The obtained polymer had a refractive index of 1.422 and a mass average molecular weight of 50,000.

[Preparation of Hollow Silica Particle Dispersion A]
Hollow silica particle fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31) in 500 parts by mass, After 30 parts by mass of acryloyloxypropyltrimethoxysilane and 1.51 parts by mass of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts by mass of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone, and obtained the dispersion liquid. Then, while adding cyclohexanone so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a dispersion A having a solid content concentration of 18.2% by mass was obtained by adjusting the concentration. . The amount of IPA remaining in the obtained dispersion A was analyzed by gas chromatography and found to be 0.5% by mass or less.

[Preparation of coating liquid A for low refractive index layer]
Each component was mixed as described below and dissolved in methyl ethyl ketone to prepare a coating solution A for a low refractive index layer having a solid content concentration of 5% by mass. The mass% of each component below is the ratio of the solid content of each component to the total solid content of the coating solution.

────────────────────────────────────────
-P-1: Perfluoroolefin copolymer (1) 15 mass%
DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 7% by mass
MF1: 5% by mass of the following fluorine-containing unsaturated compound (weight average molecular weight 1600) described in Examples of International Publication No. 2003/022906
-M-1: Nippon Kayaku Co., Ltd. KAYARAD DPHA 20 mass%
-Dispersion A: Hollow silica particle dispersion A (hollow silica particle sol surface-modified with acryloyloxypropyltrimethoxysilane, solid concentration 18.2%) 50% by mass
・ Irg127: Photopolymerization initiator Irgacure 127 (Ciba Specialty)
Chemicals Co., Ltd.) 3% by mass
────────────────────────────────────────

TD80UL (manufactured by FUJIFILM Corporation, Re / Rth = 2550/40 nm at 550 nm) was used as the support A for the surface film, and the coating liquid A for the hard coat layer having the above composition was applied to the support A for the surface film using a gravure coater. Applied. Note that TD80UL contains an ultraviolet absorber. 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. The} coating layer was cured by irradiating with an irradiation amount of 150 mJ / cm ² to form a hard coat layer A having a thickness of 12 μm.
Further, a medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution A were applied using a gravure coater. The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And the irradiation dose was 300 mW / cm ² and the irradiation dose was 240 mJ / cm ² .
The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ), And the irradiation dose was 300 mW / cm ² and the irradiation dose was 240 mJ / cm ² .
The low refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation amount was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² . Thus, the surface film A was produced.

<Preparation of optical film A>
The TD80UL surface of the produced surface film A and the optically anisotropic layer surface of the patterned optically anisotropic layer A were bonded with an adhesive to produce an optical film A.

<Preparation of polarizing plate A>
TD80UL (Re / Rth = 2550/40 nm at 550 nm manufactured by FUJIFILM Corporation) was used as the protective film A for polarizing plate A, and this surface was subjected to alkali saponification treatment. It was immersed in a 1.5 N aqueous sodium hydroxide solution at 55 ° C. for 2 minutes, washed in a water bath at room temperature, and neutralized with 0.1 N sulfuric acid at 30 ° C. Again, it was washed in a water bath and further dried with hot air at 100 ° C.
Subsequently, a roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an iodine aqueous solution and dried to obtain a polarizing film having a thickness of 20 μm. Using a 3% aqueous solution of polyvinyl alcohol (Kuraray PVA-117H) as an adhesive, the above alkali saponified TD80UL, and the same alkali saponified VA retardation film (Re / Rth = 550 nm / 550 nm, manufactured by Fujifilm) 125 nm) is sandwiched between the polarizing films so that these saponified surfaces are on the polarizing film side, and a polarizing plate A in which TD80UL and the VA retardation film serve as a protective film for the polarizing film is produced. did. At this time, the angle formed by the slow axis of the retardation film and the absorption axis of the polarizing film was made vertical.

<Preparation of polarizing plate A with optical film A>
The transparent support A surface of the optical film A prepared above and the TD80UL surface of the polarizing plate A were bonded together with an adhesive to prepare a polarizing plate A with an optical film A. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of stereoscopic display device A>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film of the polarizing plate A with optical film A produced above and an LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. With this procedure, the stereoscopic display device A having the configuration shown in FIG. The direction of the absorption axis of the polarizing film is the same as in FIG.

(Example 2)
<Preparation of patterned optically anisotropic layer AA>
After the rubbing alignment film coating solution is continuously applied with a # 8 wire bar, it is heated with 60 ° C. hot air for 60 seconds, and further with 145 ° C. (= T ₁ ) hot air (film surface temperature (= T _1S ) 125 ° C. ) For 10 minutes, and a patterned optically anisotropic layer AA was prepared in the same manner as in Example 1 except that an alignment film was formed. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P ₁ was calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.085 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 165 μm. It was. The rate of change ΔP / P ₁ was 0.055%, which was small.
Further, from the results shown in the following table, after the discotic liquid crystal is mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, A patterned optically anisotropic layer having a first retardation region and a second retardation region which are perpendicularly aligned and whose slow axes are orthogonal to each other by being aligned on the alignment film rubbed in one direction Can also be obtained.

<Preparation of surface film AA>
An optical film AA was produced in the same manner as in Example 1.

<Preparation of optical film AA>
The TD80UL surface of the produced surface film AA and the optically anisotropic layer surface of the patterned optically anisotropic layer AA were bonded together with an adhesive to produce an optical film AA.

<Preparation of polarizing plate AA>
A polarizing plate AA was produced in the same manner as in Example 1.

<Preparation of polarizing plate AA with optical film AA>
The transparent support A surface of the optical film AA produced above and the TD80UL surface of the polarizing plate AA were bonded together with an adhesive to produce a polarizing plate AA with an optical film AA. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of stereoscopic display device AA>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film and LC cell of the polarizing plate AA with optical film AA produced above were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the retardation film for VA of polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device AA having the configuration shown in FIG. The direction of the absorption axis of the polarizing film is the same as in FIG.

(Example 3)
<Preparation of patterned optically anisotropic layer AAA>
After the rubbing alignment film coating solution is continuously applied with a # 8 wire bar, it is heated with 60 ° C. hot air for 60 seconds, and further with 145 ° C. (= T ₁ ) hot air (film surface temperature (= T _1S ) 125 ° C. ), And a patterned optically anisotropic layer AAA was prepared in the same manner as in Example 1 except that an alignment film was formed. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P ₁ was calculated. The total pitch P ₂ of 1050 stripes of the optically anisotropic layer is 299.01 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 240 μm. It was. The rate of change ΔP / P ₁ was 0.08%, which was small.
Further, from the results shown in the following table, after the discotic liquid crystal is mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, A patterned optically anisotropic layer having a first retardation region and a second retardation region which are perpendicularly aligned and whose slow axes are orthogonal to each other by being aligned on the alignment film rubbed in one direction Can also be obtained.

<Preparation of surface film AAA>
An optical film AAA was produced in the same manner as in Example 1.

<Preparation of optical film AAA>
The TD80UL surface of the produced surface film AAA and the optically anisotropic layer surface of the patterned optically anisotropic layer AAA were bonded together with an adhesive to produce an optical film AAA.

<Preparation of polarizing plate AAA>
A polarizing plate AAA was prepared in the same manner as in Example 1.

<Preparation of polarizing plate AAA with optical film AAA>
The transparent support A surface of the produced optical film AAA and the TD80UL surface of the polarizing plate AAA were bonded together with an adhesive to prepare a polarizing plate AAA with the optical film AAA. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of 3D display device AAA>
The polarizing plate on the viewer side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film of the above-prepared polarizing plate AAA with optical film AAA and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the retardation film for VA of polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display AAA having the configuration shown in FIG. The direction of the absorption axis of the polarizing film is the same as in FIG.

Example 4
<Transparent support B>
TD80UL (manufactured by FUJIFILM Corporation) was prepared and used as the transparent support B. The film thickness of TD80UL was 80 μm, contained an ultraviolet absorber, the in-plane retardation Re (550) was 2 nm, and the thickness direction retardation Rth (550) was 40 nm. Further, Tg of the transparent support B was about 180 ° C.

<Preparation of patterned optically anisotropic layer B>
The transparent support A was changed to the transparent support B, and the rubbing alignment film coating solution was continuously applied with a # 8 wire bar, and then heated with hot air of 60 ° C. for 60 seconds, and further 145 ° C. (= T ₁ ). The patterned optically anisotropic layer B was prepared in the same manner as in Example 1 except that it was dried with warm air (film surface temperature (= T _1S ) 125 ° C.) for 2 minutes to form an alignment film. went. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

────────────────────────────────────────
Composition for alignment layer ────────────────────────────────────────
3.9 parts by mass of polymer material for alignment film (PVA103, Kuraray Co., Ltd. polyvinyl alcohol)
Photoacid generator (I-33) 0.1 parts by weight Methanol 36 parts by weight Water 60 parts by weight ─────────────────────────── ────────────

The first retardation region and the second retardation region of the formed patterned optically anisotropic layer B are each analyzed by TOF-SIMS (time-of-flight secondary ion mass spectrometry, TOF-SIMS V manufactured by ION-TOF). As a result, in the first retardation region and the second retardation region, the abundance ratio of the photoacid generator I-33 in the corresponding alignment layer is 10:90, and almost no I-33 is present in the first retardation region. It turns out that it has decomposed. In the optically anisotropic layer, the anion BF _{4 of} the acid HBF ₄ generated from the cation of the alignment film interface aligning agent (II-1) and the photoacid generator I-33 is formed at the air interface of the first retardation region. ^- it was confirmed that exists. These ions were hardly observed at the air interface in the second retardation region, and it was found that II-1 cations and Br ⁻ were present in the vicinity of the alignment film interface. The abundance ratio of each ion at the air interface was 93: 7 for II-1 cations and 90:10 for BF ₄ ⁻ . From this, the alignment film interface aligning agent (II-1) is unevenly distributed at the alignment film interface in the second retardation region, but the uneven distribution is decreased in the first retardation region and diffused to the air interface. In the first retardation region, it can be understood that diffusion of the II-1 cation is promoted by anion exchange between the generated acid HBF ₄ and II-1.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P ₁ was calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.235 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 15 μm. It was. The rate of change ΔP / P ₁ was 0.005%, which was remarkably small.
Further, from the results shown in the following table, after the discotic liquid crystal is mask-exposed to a PVA rubbing alignment film containing a photoacid generator in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, A patterned optically anisotropic layer having a first retardation region and a second retardation region which are perpendicularly aligned and whose slow axes are orthogonal to each other by being aligned on the alignment film rubbed in one direction Can also be obtained.

<Preparation of optical film B>
An antireflection film was formed on the surface of TD80UL of the patterned optically anisotropic layer B by the same method as in Example 1 to prepare an optical film B.

<Preparation of polarizing plate B with optical film B>
The patterned optically anisotropic layer B surface of the produced optical film B and the TD80UL surface of the polarizing plate A produced in Example 1 were bonded with an adhesive to produce a polarizing plate B with an optical film B. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer B and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of stereoscopic display device B>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Corporation was peeled off, and the retardation film for VA of the polarizing plate B with optical film B produced above and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device B having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Example 5)
<Preparation of transparent support C>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
────────────────────────────────────────
Composition of cellulose acetate solution ────────────────────────────────────────
Cellulose acetate having an acetylation degree of 60.7 to 61.1% 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) 336 parts by weight Methanol (second solvent) 29 parts 1-butanol (third solvent) 11 parts ───────────────────────────── ───────────

  In another mixing tank, 16 parts by mass of the following retardation increasing agent (A), 92 parts by mass of methylene chloride and 8 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution. A dope was prepared by mixing 474 parts by mass of the cellulose acetate solution with 25 parts by mass of the retardation increasing agent solution and stirring sufficiently. The addition amount of the retardation increasing agent was 6.0 parts by mass with respect to 100 parts by mass of cellulose acetate.

  The obtained dope was cast using a band stretching machine. After the film surface temperature on the band reaches 40 ° C., the film is dried with warm air of 70 ° C. for 1 minute, and the film from the band is dried with 140 ° C. drying air for 10 minutes, and the residual solvent amount is 0.3% by mass. A transparent support C was prepared.

  The thickness of the obtained transparent support C was 80 μm. The in-plane retardation (Re) was 8 nm and the thickness direction retardation (Rth) was 78 nm. The Tg of the transparent support C was about 180 ° C.

<Preparation of transparent support with rubbing alignment film>
The produced transparent support C was subjected to a saponification treatment, followed by heat treatment with warm air of 145 ° C. (= T ₁ ) (film surface temperature (= T _1S ) 125 ° C.) for 10 minutes. Next, a 4% aqueous solution of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. was applied to the surface subjected to saponification treatment with a No. 12 bar and dried at 80 ° C. for 5 minutes. Thereafter, one reciprocating rubbing treatment was performed in one direction at 400 rpm to produce a transparent support with a rubbing alignment film. The alignment film had a thickness of 0.5 μm.

<Preparation of patterned optically anisotropic layer C>
After preparing the following optical anisotropic layer composition, it is filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid for the optical anisotropic layer. The coating solution was applied and dried at a film surface temperature of 80 ° C. for 1 minute to obtain a liquid crystal phase and uniformly aligned, and then cooled to room temperature. Next, the stripe mask is held so that the stripe is 45 ° with respect to the rubbing direction, and a stripe mask having a horizontal stripe width of 285 μm in the transmission portion and a horizontal stripe width of 285 μm in the shielding portion (1050 stripes: total pitch) P ₁ is arranged 299.25Mm) on the application of the optically anisotropic layer coating liquid, an ultraviolet ray using a 20 mW / cm ² of air-cooled metal halide lamp under an air Ltd. (eye graphics Co.) Irradiation was performed for 5 seconds, and the first retardation region was formed by fixing the alignment state. Subsequently, the film surface temperature was raised to 140 ° C., and after making it isotropic phase, the temperature was lowered to 100 ° C. and heated at that temperature for 1 minute for uniform orientation. After cooling to room temperature, the entire surface was irradiated at 20 mW / cm ² for 20 seconds to fix the orientation state, thereby forming a second retardation region. The slow axes of the first retardation region and the second retardation region were orthogonal to each other, and the film thickness was 0.9 μm.

─────────────────────────────────────
Composition for optically anisotropic layer --------------------------------
Discotic liquid crystal E-2 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-2) 0.4 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by weight Methyl ethyl ketone 400 parts by weight ───────────────────────── ────────────

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P ₁ was calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.205 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 45 μm. It was. The rate of change ΔP / P ₁ was 0.015%, which was small.
Further, from the results shown in the following table, the discotic liquid crystal is aligned on a PVA-rubbed alignment film that has been rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature It can also be understood that a patterned optically anisotropic layer having a first retardation region and a second retardation region having a vertical orientation and perpendicular to the slow axis can be obtained by exposing with changing the phase difference. .

<Preparation of polarizing plate C>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film having a thickness of 20 μm. A transparent support C having a retardation film for VA (Re / Rth at 550 nm = 50 nm / 125 nm, manufactured by FUJIFILM) and a patterned optically anisotropic layer C subjected to alkali saponification treatment in the same manner as in Example 1. Then, a polarizing plate C in which a transparent support C of a VA retardation film and a patterned optically anisotropic layer C is a protective film for the polarizing film was prepared by sandwiching the polarizing film with an adhesive. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer C and the absorption axis of the polarizing film was set to ± 45 degrees.

<Preparation of polarizing plate C with surface film A>
The TD80UL surface of the surface film A prepared in Example 1 and the patterned optically anisotropic layer C surface of the polarizing plate C were bonded together with an adhesive to prepare the polarizing plate C with the surface film A.

<Production of stereoscopic display device C>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the retardation film for VA of the produced polarizing plate C with surface film A and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device C having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Example 5-1)
<Preparation of patterned optically anisotropic layer C-1>
Except that the transparent support C produced in Example 5 was subjected to a saponification treatment and then heat-treated with warm air of 125 ° C. (= T ₁ ) (film surface temperature (= T _1S ) 105 ° C.) for 2 minutes. A patterned optically anisotropic layer C-1 was prepared in the same manner as in No. 5. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth.
The tilt angle on the alignment film side and the air interface is vertical, and in the slow axis direction, the heat treatment at 80 ° C. is −45 °, the treatment at 140 ° C. is + 45 °, Re is 130 nm, and Rth is −65 nm. .

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P _{1 was} calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.175 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 75 μm. It was. The rate of change ΔP / P ₁ was 0.025%, which was small.

(Example 5-2)
<Preparation of patterned optically anisotropic layer C-2>
The transparent support C produced in Example 5 was subjected to saponification treatment, and then heat-treated with warm air of 100 ° C. (= T ₁ ) (film surface temperature (= T _1S ) 80 ° C.) for 60 minutes. A patterned optically anisotropic layer C-1 was prepared in the same manner as in No. 5. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth.
The tilt angle on the alignment film side and the air interface is vertical, and in the slow axis direction, the heat treatment at 80 ° C. is −45 °, the treatment at 140 ° C. is + 45 °, Re is 130 nm, and Rth is −65 nm. .

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P _{1 was} calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.175 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 75 μm. It was. The rate of change ΔP / P ₁ was 0.025%, which was small.

(Example 5-3)
<Preparation of patterned optically anisotropic layer C-2>
Except that the transparent support C produced in Example 5 was subjected to saponification treatment and then heat-treated with warm air of 155 ° C. (= T ₁ ) (film surface temperature (= T _1S ) 140 ° C.) for 2 minutes. A patterned optically anisotropic layer C-1 was prepared in the same manner as in No. 5. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth.
The tilt angle on the alignment film side and the air interface is vertical, and in the slow axis direction, the heat treatment at 80 ° C. is −45 °, the treatment at 140 ° C. is + 45 °, Re is 130 nm, and Rth is −65 nm. .

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ −P _{1 was} calculated. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.175 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 75 μm. It was. The rate of change ΔP / P ₁ was 0.025%, which was small.

(Example 6)
<Preparation of patterned optically anisotropic layer CC>
Except that the transparent support C produced in Example 5 was subjected to saponification treatment and then subjected to heat treatment with warm air of 145 ° C. (= T ₁ ) (film surface temperature (= T _1S ) 125 ° C.) for 2 minutes. A patterned optically anisotropic layer CC was prepared in the same manner as in No. 5. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.175 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 75 μm. It was. The rate of change ΔP / P ₁ was 0.025%, which was small.
Further, from the results shown in the following table, the discotic liquid crystal is aligned on a PVA-rubbed alignment film that has been rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature It can also be understood that a patterned optically anisotropic layer having a first retardation region and a second retardation region having a vertical orientation and perpendicular to the slow axis can be obtained by exposing with changing the phase difference. .

<Preparation of polarizing plate CC>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film having a thickness of 20 μm. A transparent support C of a retardation film for VA (Re / Rth = 550 nm / 125 nm at 550 nm, manufactured by FUJIFILM) and a patterned optically anisotropic layer CC subjected to alkali saponification treatment in the same manner as in Example 1. Then, a polarizing plate CC in which the transparent support C of the VA retardation film and the patterned optically anisotropic layer CC is a protective film for the polarizing film was prepared by sandwiching the polarizing film with an adhesive. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer CC and the absorption axis of the polarizing film was ± 45 degrees.

<Preparation of polarizing plate CC with surface film A>
The TD80UL surface of the surface film A prepared in Example 1 and the patterned optically anisotropic layer CC surface of the polarizing plate CC were bonded together with an adhesive to prepare a polarizing plate CC with the surface film A.

<Production of stereoscopic display device CC>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film and LC cell of the polarizing plate CC with surface film A produced above were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display CC having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Example 7)
<Preparation of patterned optically anisotropic layer CCC>
A patterned optically anisotropic layer CCC was prepared in the same manner as in Example 5 except that the optically anisotropic layer coating solution was changed to the following composition. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.8 μm.
────────────────────────────────────
Composition for optically anisotropic layers ─────────────────────────────────────
Discotic liquid crystal E-3 100 parts by mass alignment film interface alignment agent (II-1) 1.0 part by mass air interface alignment agent (P-1) 0.3 part by mass photopolymerization initiator 3.0 parts by mass (Irgacure 907 , Manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9.9 parts by mass Methyl ethyl ketone 400 mass ────────────────────────────────────

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.205 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 45 μm. It was. The rate of change ΔP / P ₁ was 0.015%, which was small.
Further, from the results shown in the following table, the discotic liquid crystal is aligned on a PVA-rubbed alignment film that has been rubbed in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer, and the heating temperature It can also be understood that a patterned optically anisotropic layer having a first retardation region and a second retardation region having a vertical orientation and perpendicular to the slow axis can be obtained by exposing with changing the phase difference. .

<Preparation of polarizing plate CCC>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film having a thickness of 20 μm. A transparent support C of a retardation film for VA (Re / Rth = 550 nm / 125 nm at 550 nm, manufactured by FUJIFILM) and a patterned optically anisotropic layer CCC subjected to alkali saponification treatment in the same manner as in Example 1. Then, a polarizing plate CCC in which the transparent support C of the VA retardation film and the patterned optically anisotropic layer CC is a protective film for the polarizing film was prepared by sandwiching the polarizing film with an adhesive. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer CCC and the absorption axis of the polarizing film was ± 45 degrees.

<Preparation of polarizing plate CCC with surface film A>
The TD80UL surface of the surface film A prepared in Example 1 and the patterned optically anisotropic layer CCC surface of the polarizing plate CCC were bonded together with an adhesive to prepare a polarizing plate CCC with the surface film A.

<Production of stereoscopic display device CCC>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the retardation film for VA of the produced polarizing plate CCC with surface film A and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device CCC having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Example 8)
<Preparation of transparent support with rubbing alignment film>
(1) Preparation of parallel alignment film (first alignment film) After subjecting the transparent support B prepared in Example 4 to saponification treatment, hot air (film surface temperature (= T _1S ) at 145 ° C. (= T ₁ ) ) 125 ° C.) for 10 minutes. On the surface subjected to the saponification treatment, a 4% water / methanol solution (PVA103 (4.0 g)) of polyvinyl alcohol “PVA103” manufactured by Kuraray Co., Ltd. was dissolved in 72 g of water and 24 g of methanol, with a viscosity of 4.35 cp and a surface tension of 44. .8 dyne) was applied with a No. 12 bar and dried at 80 ° C. for 5 minutes.

(2) Preparation of patterning orthogonal alignment film (second alignment film) 2.0 g of polyacrylic acid (Mw25000) manufactured by Wako Pure Chemical Industries, Ltd. 2.52 g of triethylamine / 1.12 g of water / 5.09 g of propanol / 3-methoxy-1 -It dissolved in 5.09g of butanol, and prepared the coating liquid.

  Next, as the flexographic plate, a synthetic rubber-like flexographic plate having irregularities having the shape shown in FIG. 7 was produced.

A flexoproof 100 (RK Print Coat Instruments Ltd. UK) was used as the flexographic printing apparatus shown in FIG. The anilox roller used was 400 cells / cm (volume: 3 cm ³ / m ² ). The flexographic plate was attached to a pressure drum of the flexoproof 100 with a pressure sensitive tape. After the parallel alignment film was affixed to the printing roller, the patterning orthogonal alignment film coating solution was put into a doctor blade, and the orthogonal alignment film was pattern-printed on the parallel alignment film at a printing speed of 30 m / min.

(3) Preparation of rubbing alignment layer After drying at 80 ° C. for 5 minutes, a reciprocating rubbing treatment was performed at 1000 rpm in a 45 ° direction with respect to the stripe line of the pattern to prepare a rubbing alignment layer.

<Preparation of patterned optically anisotropic layer D>
The coating solution for optical anisotropy prepared in Example 5 was applied, dried at a film surface temperature of 110 ° C. for 1 minute to obtain a liquid crystal phase, cooled to 80 ° C., and air-cooled at 160 W / cm in air. An attempt was made to fabricate a patterned optically anisotropic layer D by irradiating ultraviolet rays using a metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to fix the orientation state. The film thickness of the optically anisotropic layer was 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in Table 1. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.22 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 30 μm. It was. The rate of change ΔP / P ₁ was 0.01%, which was small.
Further, from the results shown in the following table, a PVA rubbing alignment film (first alignment film) obtained by rubbing a discotic liquid crystal in one direction in the presence of a pyridinium salt compound and a fluoroaliphatic group-containing copolymer. / By aligning and exposing on a polyacrylic acid-based rubbing alignment film (second alignment film), it has a first retardation region and a second retardation region that are vertically aligned and whose slow axes are orthogonal to each other. It can be seen that a patterned optically anisotropic layer is obtained.

<Preparation of optical film D>
An antireflection film was formed on the surface of the transparent support B of the patterned optically anisotropic layer D by the same method as in Example 1 to produce an optical film D.

<Preparation of polarizing plate D with optical film D>
TD80UL (manufactured by FUJIFILM Corporation, Re / Rth at 550 nm = 2 nm / 40 nm) was used as a protective film D for polarizing plate D, and this surface was subjected to alkali saponification treatment. It was immersed in a 1.5 N aqueous sodium hydroxide solution at 55 ° C. for 2 minutes, washed in a water bath at room temperature, and neutralized with 0.1 N sulfuric acid at 30 ° C. Again, it was washed in a water bath and further dried with hot air at 100 ° C.
Subsequently, a rolled polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film having a thickness of 20 μm. Using a 3% aqueous solution of polyvinyl alcohol (Kuraray PVA-117H) as an adhesive, the above-mentioned alkali saponified TD80UL is bonded to one side of the polarizing film so that the saponified surface is on the polarizing film side. Attached the patterned optically anisotropic layer D surface of the optical film D via an adhesive. In this manner, a polarizing plate D in which TD80UL and the optical film D are protective films for the polarizing film was produced. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of stereoscopic display device D>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film of the polarizing plate D with the optical film D and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device D having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

Example 9
<Preparation of transparent support A with photo-alignment film>
A 1% aqueous solution of photoalignment material E-1 having the following structure was applied to the saponified surface of the transparent support A produced in Example 1, and dried at a film surface temperature (= T _1S ) of 125 ° C. for 60 minutes. . The obtained coating film was irradiated with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm ² under air. At this time, as shown in FIG. 9A, a wire grid polarizer (Moxtek, ProFlux PPL02) is set in direction 1, and mask A (transmission part horizontal stripe width 285 μm, shielding part horizontal stripe). Exposure was performed through a stripe mask having a width of 285 μm (1050 stripes: total pitch (P ₁ ) 299.25 mm). Thereafter, as shown in FIG. 9B, a wire grid polarizer is set in direction 2, and exposure is further performed through a mask B (a stripe mask having a lateral stripe width of 285 μm at the transmission portion and a lateral stripe width of 285 μm at the shielding portion). Went. The distance between the exposure mask surface and the photo-alignment film was set to 200 μm. The illuminance of ultraviolet rays used at this time was 100 mW / cm ² in the UV-A region (integration of wavelengths 380 nm to 320 nm), and the irradiation amount was 1000 mJ / cm ² in the UV-A region.

<Preparation of patterned optically anisotropic layer E>
After preparing the following composition for optically anisotropic layers, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution. The coating solution is applied onto the transparent support A with a photo-alignment film, dried at a film surface temperature of 105 ° C. for 2 minutes to form a liquid crystal phase, cooled to 75 ° C., and 160 W / cm ² under air. An attempt was made to produce a patterned optically anisotropic layer E by irradiating with ultraviolet rays using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) to fix the orientation state. The film thickness of the optically anisotropic layer was 1.3 μm.

────────────────────────────────────────
Composition for optically anisotropic layers ────────────────────────────────────────
Rod-shaped liquid crystal (LC242, manufactured by BASF Corporation) 100 parts by mass horizontal alignment agent A 0.3 parts by mass photopolymerization initiator 3.3 parts by mass (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.1 parts by weight Methyl ethyl ketone 300 parts by weight ───────────────────────── ───────────────

(Evaluation of optically anisotropic layer)
The distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the rod-like liquid crystal at the alignment film interface, the air interface The tilt angle of the rod-like liquid crystal, the direction of the slow axis, and Re and Rth were measured. The results are shown in the table below. In the following table, horizontal represents a tilt angle of 0 ° to 20 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer is 299.19 mm, while the total pitch P ₁ of the stripe mask is 299.25 mm, which is almost unchanged, but is shortened by 60 μm. It was. The rate of change ΔP / P ₁ was 0.02%, which was small.
Further, from the results shown in the following table, the first retardation region and the second retardation region in which the rod-like liquid crystal is aligned on the photo-alignment film and exposed to be horizontally aligned and the slow axes are orthogonal to each other. It can be seen that a patterned optically anisotropic layer having

<Preparation of optical film E>
An antireflection film was formed on the surface of the transparent support A of the patterned optically anisotropic layer E in the same manner as in Example 1 to produce an optical film E.

<Preparation of polarizing plate E with optical film E>
The patterned optically anisotropic layer E surface of the produced optical film E and the TD80UL surface of the polarizing plate A produced in Example 1 were bonded together with an adhesive to produce a polarizing plate E with an optical film E. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer E and the absorption axis of the polarizing film was ± 45 degrees.

<Production of stereoscopic display device E>
The polarizing plate on the viewing side of FlexScan S2231 manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film of the polarizing plate E with optical film E produced above and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device E having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Comparative Example 1)
<Preparation of patterned optically anisotropic layer a>
The coating solution for rubbing alignment film was continuously applied with a # 8 wire bar and then dried for 60 seconds with hot air at 70 ° C. (film surface temperature 60 ° C.) to form an alignment film. The optically anisotropic layer a patterned by the operation was prepared. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer was 298.95 mm, while the total pitch P ₁ of the stripe mask was 299.25 mm, which was 300 μm shorter. The rate of change ΔP / P ₁ was 0.1%.

<Preparation of surface film a>
An optical film a was produced in the same manner as in Example 1.

<Preparation of optical film a>
The TD80UL surface of the produced surface film a and the optically anisotropic layer surface of the patterned optically anisotropic layer a were bonded with an adhesive to produce an optical film a.

<Preparation of polarizing plate a>
A polarizing plate a was produced in the same manner as in Example 1.

<Preparation of polarizing film a with optical film a>
The transparent support A surface of the optical fill a and the TD80UL surface of the polarizing plate a were bonded together with an adhesive to prepare a polarizing plate a with an optical film a. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of stereoscopic display device a>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film and LC cell of the polarizing plate a with optical film a produced above were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device a having the configuration shown in FIG. The direction of the absorption axis of the polarizing film is the same as in FIG.

(Comparative Example 2)
<Preparation of patterned optically anisotropic layer b>
The coating solution for rubbing alignment film was continuously applied with a # 8 wire bar and then dried for 60 seconds with hot air at 70 ° C. (film surface temperature 60 ° C.) to form the alignment film, and the same as in Example 4. The optically anisotropic layer b patterned by the operation was prepared. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer was 298.95 mm, while the total pitch P ₁ of the stripe mask was 299.25 mm, which was 300 μm shorter. The rate of change ΔP / P ₁ was 0.1%.

<Preparation of optical film b>
An antireflection film was formed on the surface of TD80UL of the patterned optically anisotropic layer b by the same method as in Example 1 to produce an optical film b.

<Preparation of polarizing plate b with optical film b>
The patterned optically anisotropic layer b surface of the produced optical film b and the TD80UL surface of the polarizing plate A produced in Example 1 were bonded together with an adhesive to produce a polarizing plate b with an optical film b. At this time, the angle formed by the slow axis of the patterned optically anisotropic layer b and the absorption axis of the polarizing film was set to ± 45 degrees.

<Production of stereoscopic display device b>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film and LC cell of the polarizing plate b with optical film b produced above were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the retardation film for VA of polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device b having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Comparative Example 3)
<Preparation of patterned optically anisotropic layer c>
The transparent support C produced in Example 5 was subjected to saponification treatment and then patterned in the same manner as in Example 5 except that it was dried with warm air at 70 ° C. (film surface temperature 60 ° C.) for 10 minutes. An optically anisotropic layer c was prepared. The alignment film had a thickness of 0.5 μm, and the optically anisotropic layer had a thickness of 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer was 298.95 mm, while the total pitch P ₁ of the stripe mask was 299.25 mm, which was 300 μm shorter. The rate of change ΔP / P ₁ was 0.1%.

<Preparation of polarizing plate c>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm was continuously stretched 5 times in an aqueous iodine solution and dried to obtain a polarizing film having a thickness of 20 μm. A transparent support C having a retardation film for VA (Re / Rth at 550 nm = 50 nm / 125 nm, manufactured by Fuji Film) and a patterned optically anisotropic layer c subjected to alkali saponification treatment in the same manner as in Example 1. Then, the polarizing film was bonded with an adhesive across the polarizing film, and a polarizing plate c in which the transparent support C of the optically anisotropic layer c patterned with the retardation film for VA was a protective film for the polarizing film was produced. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer c and the absorption axis of the polarizing film was set to ± 45 degrees.

<Preparation of polarizing film c with surface film A>
The TD80UL surface of the surface film A prepared in Example 1 and the patterned optically anisotropic layer c surface of the polarizing plate c were bonded together with an adhesive to prepare a polarizing plate c with the surface film A.

<Production of stereoscopic display device c>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film and LC cell of the produced polarizing plate c with surface film A were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device c having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Comparative Example 4)
<Preparation of patterned optically anisotropic layer d>
(1) Preparation of parallel alignment film (first alignment film) Transparent support B prepared in Example 4 was subjected to saponification treatment and then heat-treated for 10 minutes with 70 ° C warm air (film surface temperature 60 ° C). Except for the above, a patterned optically anisotropic layer d was prepared by the same operation as in Example 8. The film thickness of the optically anisotropic layer was 0.9 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer was 298.95 mm, while the total pitch P ₁ of the stripe mask was 299.25 mm, which was 300 μm shorter. The rate of change ΔP / P ₁ was 0.1%.

<Preparation of optical film d>
An antireflection film was formed on the surface of the transparent support B of the patterned optically anisotropic layer d by the same method as in Example 1 to produce an optical film d.

<Preparation of polarizing film d with optical film d>
A polarizing plate d with an optical film d was produced in the same manner as in Example 8.

<Production of stereoscopic display device d>
The polarizing plate on the viewing side of FlexScan S2231W manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film and LC cell of the polarizing plate d with optical film d produced above were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device d having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

(Comparative Example 5)
<Preparation of patterned optically anisotropic layer e>
Example 1 except that a 1% aqueous solution of the photo-alignment material E-1 of Example 9 was applied to the saponified surface of the transparent support A produced in Example 1 and dried at a film surface temperature of 60 ° C. for 60 minutes. The optically anisotropic layer e patterned by the same operation as 9 was produced. The film thickness of the optically anisotropic layer was 1.3 μm.

(Evaluation of optically anisotropic layer)
In the same manner as in Example 1, the distance (total pitch P ₂ ) of 1050 stripes of the produced optically anisotropic layer was measured using Quick Vision Pro manufactured by Mitutoyo Corporation.
Next, after peeling off the produced optically anisotropic layer from the transparent support, according to the above method using KOBRA-21ADH (manufactured by Oji Scientific Instruments), the tilt angle of the discotic liquid crystal at the alignment film interface, the air interface The discotic liquid crystal was measured for the tilt angle, the direction of the slow axis, and Re and Rth. The results are shown in the table below. In the following table, “vertical” represents a tilt angle of 70 ° to 90 °.

The total pitch P ₂ for 1050 stripes of the optically anisotropic layer and the total pitch P ₁ of the stripe mask were measured, and the difference P ₂ -P ₁ is shown in the following table. The total pitch P ₂ for 1050 stripes of the optically anisotropic layer was 298.95 mm, while the total pitch P ₁ of the stripe mask was 299.25 mm, which was 300 μm shorter. The rate of change ΔP / P ₁ was 0.1%.

<Preparation of optical film e>
An antireflection film was formed on the surface of the transparent support A of the patterned optically anisotropic layer e by the same method as in Example 1 to produce an optical film e.

<Preparation of polarizing plate e with optical film e>
The patterned optical anisotropic layer e surface of the produced optical film e and the TD80UL surface of the polarizing plate A produced in Example 1 were bonded together with an adhesive to produce a polarizing plate e with an optical film e. At this time, the angle formed between the slow axis of the patterned optically anisotropic layer E and the absorption axis of the polarizing film was ± 45 degrees.

<Production of stereoscopic display device e>
The polarizing plate on the viewing side of FlexScan S2231 manufactured by Nanao Co., Ltd. was peeled off, and the VA retardation film of the polarizing plate e with the optical film e and the LC cell were bonded together with an adhesive. Subsequently, the polarizing plate on the light source side was peeled off, and the VA retardation film of the polarizing plate A and the LC cell were bonded together with an adhesive. A stereoscopic display device e having the configuration shown in FIG. The direction of the absorption axis of the polarizing film was the same as in FIG.

<Evaluation of stereoscopic display device>
Each stereoscopic display device displaying a stereoscopic image in which right-eye / left-eye images having parallax were alternately arranged was observed through 3D glasses from 0 degree polar angle, and the degree of crosstalk was evaluated in 7 stages. Subsequently, the observation was made from polar angles of 45 degrees with azimuth angles of 0 degrees and 180 degrees, and the same evaluation was performed. Subsequently, observation was performed from a polar angle of 5 degrees with an azimuth angle of 90 degrees and 270 degrees, and the same evaluation was performed. Evaluation was carried out in 7 stages from 7 (no crosstalk) to 1 (large crosstalk). The results are shown in Table 2 below.

12 Optically anisotropic layer (patterned retarder layer)
14 Alignment film 16 Film 18 Linearly polarizing film

Claims (8)

A method for producing a film / patterned retarder having at least a film and a patterned retarder layer thereon, comprising the following 1) to 3)
1) Step of heating the film at T ₁ satisfying Tg−100 <T ₁ <Tg (where Tg is a glass transition point of the film) 2) On the surface of the film, liquid crystal is contained as a main component. A step of applying a composition to form a coating film, and 3) a step of aligning liquid crystals by heating the coating film,
In this order, a method for producing a film-patterned retarder. 1) The method according to claim 1, wherein the step is a step of setting the film surface temperature T _1s of the film to Tg−120 ° C. ≦ T _1S ° C. ≦ Tg−20 ° C. The method according to claim 1 or 2, wherein the step 1) is a step of heating the cellulose acylate film to bring the film surface temperature of the film to 80 ° C to 150 ° C. The method according to any one of claims 1 to 3, further comprising a step of performing mask exposure after the step. The total pitch P ₁ of the mask used to mask exposure, the ratio [Delta] P / P ₁ of the difference [Delta] P between the total pitch P ₂ of the patterned retarder (= P ₁ -P ₂₎ is less than 0.1% according Item 5. The method according to Item 4. 6. The step of mask exposure is a step of forming a pattern alignment film in which first and second alignment control regions each having an alignment ability for aligning the major axis of liquid crystal in different directions are arranged alternately. The method described in 1. 3) The method according to any one of claims 1 to 6, further comprising a step of fixing the alignment of the liquid crystal after the step. A first retarder region and a second retarder region having mutually different in-plane slow axis directions are included, and the first and second retarder regions have patterned retarder layers arranged alternately in a plane. The method of any one of Claims 1-7 which is a manufacturing method of a film patterned retarder.

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