TWI407212B - Film, process for producing film, and use thereof - Google Patents

Abstract

A film that exhibits the highest refractive index in an oblique direction against film plane, the direction being arbitrarily changeable; a process for producing such a film; and use thereof. A layer of rodlike polymerizable liquid crystal compound of homogeneous alignability is formed on a vertical alignment film. At the stage of the formation, the rodlike polymerizable liquid crystal compound undergoes a tilt alignment at the interface of the vertical alignment film. Further, at that stage, the tilt angle can be easily regulated through the degree of rubbing treatment for the vertical alignment film. That is, the tilt angle of index ellipsoid in an optically anisotropic layer can be arbitrarily controlled. Therefore, the refractive index is the highest in an oblique direction against film plane, and the direction can be arbitrarily changed.

Description

Film and film manufacturing method, and use thereof

The present invention relates to a method for producing a film and a film, and to a user thereof, and to a method for producing a film and a film which change a refractive index in an oblique direction with respect to a plane of a film, and to an application thereof.

A flat panel display device (hereinafter referred to as "FPD") such as a liquid crystal display device (hereinafter also referred to as "LCD") or an organic electroluminescence (hereinafter referred to as "EL") is associated with a CRT. The comparison system can save space and low power consumption. Therefore, in recent years, FPD has been widely and widely used as a screen for computers, televisions, mobile phones, navigators or data terminals.

In the FPD, a wide variety of optical films are generally used in order to prevent reflection, enlarge the viewing angle, and the like. The optical film is, for example, an antireflection film such as an antireflection (hereinafter also referred to as "AR") film which is formed by multilayering an optical film layer having a different refractive index and reducing the reflectance of the surface by the interference effect of light. A polarizing film that transmits only light in a specific vibration direction and shields other light, and a phase difference film that optically compensates for an interference color of an LCD such as an STN method or a TN method, and integrates the polarizing film and the retardation film. The elliptically polarizing film and the viewing angle-expanding film which expands the viewing angle of the LCD.

Further, the optical film used for the FPD varies depending on the type of FPD to which it is applied. For example, when an optical compensation film having a wide viewing angle is displayed in an LCD, it varies depending on the driving method of the LCD.

Specifically, in the VA mode LCD, optical compensation can be performed by using an extension film that changes the refractive index in the planar direction. As the above-mentioned stretched film, a film which has been used as a retardation film which imparts an optical compensation effect since ancient times can be used. The above-mentioned stretched film can be obtained, for example, by stretching a film of polyvinyl alcohol or polycarbonate.

Further, in the TN mode LCD, in order to develop a wide viewing angle, it is preferable to use an optical film which changes the refractive index in an oblique direction. Such a film may, for example, be a WV film (trade name, manufactured by Fuji Photo Film Co., Ltd.) or an NH film (trade name, manufactured by Nippon Oil Co., Ltd.). These films are not stretch films and are optical compensation films that utilize the oblique alignment of liquid crystal molecules. The above liquid crystal molecules are obliquely aligned liquid crystal molecules which are horizontally aligned at the interface of the alignment film and vertically aligned at the air interface. Thereby, the obtained film is a film which changes the refractive index in an oblique direction.

Other techniques relating to an optical film that changes the refractive index in an oblique direction include, for example, the techniques disclosed in Patent Documents 1 and 2. Specifically, Patent Document 1 discloses a liquid crystalline polymer film which is applied to a substrate for alignment, first uniformly coating a liquid crystalline polymer, and then heat-treating at a liquid crystal temperature of the polymer to tilt After the alignment, the person is cooled and the tilt alignment state is fixed. Further, it is described that the liquid crystal polymer film has an appropriate tilt angle in the range of 5° to 85°.

Further, Patent Document 2 discloses an optical film obtained by crosslinking a disk-shaped liquid crystal compound having an oxetanyl group in an alignment state formed by a liquid crystal state by light and/or heat. The person. It is described that the alignment of the discotic liquid crystal compound is preferably a hybrid orientation.

[Patent Document 1] Japanese Patent Publication No. 7-20434 (publication of January 24, 1995)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2004-109381 (published on April 8, 2004)

However, as described above, the film which changes the refractive index in the oblique direction as represented by the WV film is produced by horizontally aligning the interface between the horizontal alignment film and the alignment film, and obliquely aligning the liquid crystal molecules at the air interface. Therefore, although the refractive index can be changed in the oblique direction, the direction in which the refractive index is most varied (the inclination angle of the refractive index ellipsoid) cannot be arbitrarily controlled. In general, in order to make the viewing angle of the liquid crystal panel wide, it is assumed that the degree of optical compensation for each liquid crystal panel differs even if the liquid crystal driving method is the same. However, in such films, the tilt angle of the refractive index ellipsoid cannot be arbitrarily controlled, and thus it is impossible to achieve sufficient optical compensation for the liquid crystal panel.

In the liquid crystalline polymer film of Patent Document 1, the alignment of the liquid crystalline molecules is controlled to a wide extent. However, in the production of the above liquid crystalline polymer film, a polymer of a crystalline polymer is used. Therefore, in the case of various liquid crystal polymers disclosed herein, in order to align the crystal polymer in a single region, it is necessary to form a liquid crystal polymer in a liquid crystal state, and it is necessary to heat at a high temperature in the liquid crystal alignment step. Therefore, it is necessary to select a substrate which is durable for heat treatment. In short, in the technique of Patent Document 1, there is a problem that a substrate having low heat resistance cannot be used. Further, since the fluidity is increased with the temperature rise, the adhesion to the substrate is lowered, and the optical anisotropy is remarkably lowered by the residual stress.

In the optical film of Patent Document 2, a liquid crystal compound which is an oblique alignment (hybrid orientation) is used. When a liquid crystal compound which is such an oblique alignment is used, in order to control the tilt angle, it is necessary to change the liquid crystal compound to be used. However, in general, if any liquid crystal compound is used, it is difficult to predict the so-called tilt angle which becomes any tilt angle. Further, there are limitations on the liquid crystal compounds which can be synthesized. Therefore, it is extremely difficult to have an optical film for which the desired tilt angle is to be produced. Further, although the tilt angle of the liquid crystal compound can be controlled by an additive or the like, it is also necessary to consider the complex refractive index of the additive in the optical anisotropic layer. Therefore, in such a way, it is extremely difficult to control the tilt angle.

As described above, the wide-view optical compensation film that can be adapted to the conventional TN mode has various problems, and further development of an optical compensation film is being sought.

Moreover, in particular, in recent years, FPD is progressing toward large-scale development, and new discoveries have arisen due to the problem of optical films. Specifically, when the FPD is enlarged, when the entire display screen is viewed from a wide angle, there is a problem that so-called display image coloring (also referred to as coloring phenomenon) or white black reversal (also referred to as reversal phenomenon) occurs. Further, if the viewing angle is tilted in the direction of the reverse viewing direction in the direction above the display screen, there is a problem that the contrast is lowered. Therefore, in order to solve such a problem, the optical film is sought to provide an optical film which imparts optical anisotropy in any direction even without many erroneous attempts.

The present invention has been made in view of the above problems, and provides a method for producing a film and a film having the highest refractive index in an oblique direction with respect to a film plane, and an application thereof.

In view of the above-described problems, the inventors of the present invention have found that the layer having a homogeneous alignment of the rod-shaped polymerizable liquid crystal compound is formed by the alignment film for the vertical alignment, and the highest refractive index in the oblique direction with respect to the plane of the film can be obtained. The rate of the film is completed by the present invention. That is, the present invention encompasses the following inventions which are industrially useful.

(1) A film comprising a film forming an optical anisotropic layer on a vertical alignment alignment film, wherein the optical anisotropic layer is composed of a layer containing a polymer, and the polymer contains The structural unit of the rod-shaped polymerizable liquid crystal compound; wherein the rod-like polymerizable liquid crystal compound has a characteristic of horizontal alignment on a horizontal alignment film and horizontal alignment at an air interface, the rod-shaped polymerization The liquid crystal compound is tilted and aligned with respect to the alignment film for vertical alignment described above.

(2) The film according to (1), wherein the vertical alignment alignment film is an alignment film which is subjected to a rubbing treatment on the vertical alignment film.

(3) The film according to (1) or (2), wherein an inclination angle of the film plane with respect to the refractive index ellipsoid in the optical anisotropic layer is from 10 to 85.

(4) A film comprising a film forming an optical anisotropic layer on the alignment film for vertical alignment, wherein the optical anisotropic layer is composed of a layer containing a rod-shaped polymerizable liquid crystal compound, and the film The rod-shaped polymerizable liquid crystal compound has a characteristic of horizontal alignment on the horizontal alignment film and horizontal alignment at the air interface, and the rod-shaped polymerizable liquid crystal compound is obliquely aligned with respect to the vertical alignment alignment film.

(5) The film according to any one of (1) to (4) which exhibits a reverse wavelength dispersion.

(6) The film according to (5), wherein the optical anisotropic layer contains a polymer, and the polymer further contains a structural unit derived from a polymerizable compound represented by the following formula (1), and the formula (1) Is P2-E2-X2-B2-A2-(G2)t-Y-(G1)s-A1-B1-X1-E1-P1 (1) (wherein Y represents a divalent group, s and t Each of them is independent, representing an integer of 0 or 1, and G1 and G2 are each independently, indicating that -CR ¹ R ² -, R ¹ and R ² are independent, respectively, and represent an alkyl group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom. , A1 and A2 are independent, and represent a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group, a sulfur extended phenyl group, A1 and A2, and may also be combined with a carbon number. An alkyl group of 1 to 5, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and B1 and B2 are each independently selected from -CRR'-, -C≡C-, -CH=CH-, -CH _{2 .} -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)- O-, -C(=S)-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CH=N-,- N=CH-, -N=N-, -N(→O)=N-, -N=N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH ₂ -, -NR-, - CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, group consisting of single bonds The divalent group in the group, R and R' are each independently, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X1 and X2 are each independently, and represent the following formula (2). (wherein, A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, B3 represents the same meaning as the above B1 and B2, and n represents an integer of 1 to 4), and the E1 and E2 systems are independent. , which represents an olefin group having 2 to 25 carbon atoms, and E1 and E2 may further combine an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom, and P1 and P2 represent a hydrogen atom or a polymerizable property. The base, at least one of P1 and P2 is a polymerizable group).

(7) A method for producing a film, comprising a film having an optical anisotropic layer formed on an alignment film for vertical alignment, comprising at least the following steps: (A) an alignment film for vertical alignment a step of applying a composition containing a rod-like polymerizable liquid crystal compound, and (B) a step of heating the coating film formed in the above step (A) at 25 to 120 ° C for 10 seconds to 60 minutes; The polymerizable liquid crystal compound has a monomer which is horizontally aligned on the horizontal alignment film and which is horizontally aligned at the air interface.

(8) The method for producing a film according to (7), which further comprises (C) a step of crosslinking the rod-shaped polymerizable liquid crystal compound by photopolymerization.

(9) The method for producing a film according to (7) or (8), which further comprises (D) a step of subjecting the alignment film for vertical alignment to a rubbing treatment before the step (A).

(10) A polarizing film characterized by laminating a film according to any one of (1) to (6).

(11) A flat display device comprising the film according to any one of (1) to (6), or the polarizing film according to (10).

(12) An optical film comprising: an optical anisotropic layer composed of a liquid crystal, the optical anisotropic layer having a first surface and a second surface parallel to the first surface; and an optical anisotropic layer The alignment layer in contact with the first surface; in at least a part of the optical anisotropic layer, the liquid crystal is aligned with respect to the thickness direction, and is aligned with the first refractive index (nz) perpendicular to the first direction of the optical film, and The second refractive index (nx) in the second direction at right angles to the first direction of the optical film, and the third refractive index (ny) in the third direction at right angles to the first direction and the second direction of the optical film, The first refractive index (nz) is larger than the second refractive index (nx) and the third refractive index (ny).

Another feature of the present invention is to control the alignment of the liquid crystal layer after hardening by controlling the alignment of the monomer or oligomer (specifically, the rod-like polymerizable liquid crystal compound) for forming a liquid crystal before curing. Orientation. It is considered that the alignment of the monomer before curing is the same as that of the polymer after curing, that is, the alignment of the liquid crystal.

In the film according to the present invention, an optical anisotropic layer is formed on the vertical alignment film. The optically anisotropic layer contains a layer of a rod-like polymerizable liquid crystal compound which is horizontally aligned on a horizontal alignment film and horizontally aligned at an air interface. Therefore, the effect of arbitrarily controlling the tilt angle of the refractive index ellipsoid in the optical anisotropic layer is exerted.

(Best form of implementing the invention)

Embodiments of the present invention will be described below, but the present invention is not limited thereto.

<I. Films Related to the Invention>

The film according to the present invention has a film of the optical anisotropic layer 11 formed on the alignment film 12 for vertical alignment. The vertical alignment alignment film 12 is formed on a support substrate. That is, the film according to the present invention is formed on the support substrate, and the film of the vertical alignment alignment film 12 and the optical anisotropic layer 11 is sequentially laminated. Further, the film of the present invention is an air layer on the opposite side of the optical anisotropic layer.

The optical anisotropic layer 11 is composed of a layer containing a polymer obtained by polymerizing a rod-shaped polymerizable liquid crystal compound. As shown in Fig. 1A, the rod-shaped polymerizable liquid crystal compound has a rod-like polymerizable liquid crystal compound 14 which has a horizontal alignment on a horizontal alignment film and a horizontal alignment at an air interface. When such a rod-like polymerizable liquid crystal compound is used, the rod-shaped polymerizable liquid crystal compound is obliquely aligned with respect to the alignment film for vertical alignment. More specifically, the rod-shaped polymerizable liquid crystal compound is tilted and mixed as shown in FIG. 1B by the rubbing of the alignment film for vertical alignment, or is tilt-aligned as shown in FIG. 1C. In addition, the rod-shaped polymerizable liquid crystal compound is inclined and blended as shown in FIG. Variety. Therefore, in the film according to the present invention, the highest refractive index is present in the oblique direction with respect to the plane of the film, and the direction can be arbitrarily changed. Therefore, the film according to the present invention is used in a liquid crystal panel such as a TN mode, and can be used as a suitable optical film in order to exhibit a wide viewing angle.

In addition, in the first aspect to the first aspect, the alignment film for the vertical alignment is referred to as an "alignment layer", the rod-shaped polymerizable liquid crystal compound is referred to as "liquid crystal molecule", and the optical anisotropic layer is referred to as "liquid crystal." Floor".

Further, the film of the present invention has optical anisotropy. The above optical anisotropy may be, for example, a tilt angle, a phase difference value, or the like. The optical anisotropy of the film of the present invention will be described in detail in accordance with Fig. 2 as follows.

As shown in Fig. 2, in the refractive index ellipsoid 22 which displays the optical characteristics of the film 1, the main refractive indices na, nb, and nc of the third dimension are defined. The angle formed by the Y-axis and the main refractive index nb is defined as the inclination angle 23. When viewed from the Z direction, the vertical elliptical surface 24 formed on the film is defined as the difference between the major axis ny and the minor axis nx, ny and nx. Product with film thickness d (ny-nx). d is defined as the phase difference value.

The method of measuring the phase difference value is, for example, a method such as an ellipsometer (Ellipsometer) measurement. The measurement method of the tilt angle is, for example, in the measurement of the phase difference, by fitting the calculated value of the change in the incident angle relationship of the phase difference value of the ideal refractive index ellipsoid by measuring the incident angle relationship of the light. The method of curve fitting calculation and the like.

Generally, the phase difference is about 5 to 700 nm, preferably about 50 to 400 nm.

Hereinafter, the above-mentioned support base material, vertical alignment film, and optical anisotropic layer will be described in more detail.

(I-1) support substrate

The support substrate is not particularly limited as long as it can form an alignment film for vertical alignment on the support substrate. For example, glass, a plastic sheet, a plastic film, and a light-transmitting film can be mentioned. Moreover, the translucent film may, for example, be a polyolefin film such as polyethylene, polypropylene or a norbornene-based polymer, a polyvinyl alcohol film, a polyethylene terephthalate film or a polymethacrylate. Film, polyacrylate film, cellulose ester film, polyethylene naphthalate film, polycarbonate film, polyfluorene film, polyether enamel film, polyether ketone film, polyphenylene sulfide film, polyphenylene oxide film, etc. .

In general, the optically anisotropic layer using a polymerizable liquid crystal compound is a film, for example, a step of using a film of the present invention, a step of transporting a film, and a process of storing a film, etc., even if the film strength is a necessary step, By using the support substrate, it can be easily handled without breaking or the like.

(I-2) alignment film for vertical alignment

In the film of the present invention, the alignment film for vertical alignment has solvent resistance which is not dissolved by application of an optical anisotropic layer, and has heat resistance by heat treatment by removal of a solvent or alignment of a liquid crystal. The peeling or the like caused by rubbing or the like does not occur, and is a polymer or a composition containing a polymer.

The polymer is not particularly limited as long as it can be formed on the support substrate. For example, polyamine or gelatin having a guanamine bond in a molecule, polyimine having a ruthenium imine bond in a molecule, and a polyhydrazide, a polyvinyl alcohol, and a polypropylene thereof A polymer of guanamine, polyoxazole, polyethylenimine, polyacrylic acid, polyacrylate, or the like. These polymers may be used singly or in combination of two or more kinds, or may be a copolymer. These polymers can be easily obtained by polycondensation by dehydration, deamination or the like, or chain polymerization such as radical polymerization, anionic polymerization or cationic polymerization, coordination polymerization or ring-opening polymerization.

Further, such a polymer can be introduced with an alicyclic group such as cholesterol, a long-chain alkyl group, a fluorinated alkyl group, an aromatic ring structure, and an organic group having a fluorine-containing aromatic ring structure. By introducing the structure as described above, the rod-shaped polymerizable liquid crystal compound is more easily aligned vertically. Further, by mixing a mixture of an organic group having an alicyclic group such as cholesterol, a long-chain alkyl group, a fluorinated alkyl group, an aromatic ring structure, and an aromatic ring structure containing fluorine, or adding a cerium salt, a cerium ion, or a cerium ion The inorganic salt or the organic acid salt is used as a composition, and the rod-shaped polymerizable liquid crystal compound is also more easily aligned vertically.

Specific examples of the polymer include, for example, JP-A No. 2001-305549, WO2003-042752, JP-A-2005-139228, Liquid Crystal No. 8, No. 4, No. 216, and the like. Polyvinyl alcohol or the like disclosed in JP-A-2005-196015, JP-A-2005-315988, and JP-A-2005-196016. In addition, the polyimine alignment film for vertical alignment (trade name: SE-5300, manufactured by Nissan Chemical Co., Ltd.) used in the examples described later is also a polyimide film for vertical alignment.

The thickness of the alignment film for vertical alignment is generally from 10 nm to 10,000 nm, preferably from 10 nm to 1000 nm. If it is in the above range, the obtained film can be made lighter. Further, the optical characteristics of the alignment film for vertical alignment can reduce the influence on the obtained film.

By using the alignment film for vertical alignment described above, the rod-shaped polymerizable liquid crystal compound can be tilted to be aligned with the film plane, or tilt-aligned. Therefore, the obtained film becomes an oblique alignment film.

(I-3) Optical anisotropy layer

The optical anisotropic layer has an optically anisotropic layer formed on the alignment film for vertical alignment. The optical anisotropic layer is a layer composed of a polymer containing a structural unit derived from a rod-shaped polymerizable liquid crystal compound. The optical anisotropic layer may further contain a polymer containing a structural unit derived from a compound other than the rod-shaped polymerizable liquid crystal compound. For example, in order to impart a desired wavelength dispersion property to the film of the present invention, a polymer containing a structural unit derived from a specific polymerizable compound can be further used in the structural unit derived from the rod-shaped polymerizable liquid crystal compound. In addition, a structural unit of a liquid crystal compound in which a rod-like polymerizable liquid crystal compound and a specific polymerizable compound are different (hereinafter, referred to as "other liquid crystal compound" as described above) may be contained. Further, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a coating agent, or the like may be contained. At the same time, the content of the compound constituting the optical anisotropic layer will be described later.

The thickness of the optical anisotropic layer is such that the phase difference (delay value, Re(λ)) of the obtained film becomes a desired value, and may be appropriately adjusted. Re(λ) is determined according to the following formula (a). That is, in order to obtain the desired Re (λ), it is only necessary to adjust the film thickness d.

Re(λ)=d×Δn(λ)............(a)

(wherein, Re(λ) represents the phase difference of the wavelength λ nm, d represents the film thickness, and Δn(λ) represents the refractive index anisotropy of the wavelength λ nm.)

Further, in a preferred embodiment of the film of the present invention, the alignment film for vertical alignment is rubbed, and the refractive index ellipsoid of the rod-shaped polymerizable liquid crystal compound is at the interface of the alignment film for vertical alignment with respect to the film plane. It is preferred to have a tilt angle of 10° to 85°. Thereby, the film becomes an oblique alignment film.

Hereinafter, the rod-shaped polymerizable liquid crystal compound, other liquid crystal compound, polymerizable compound, and other constituent compounds which may be contained in the above-mentioned optical anisotropic layer will be described in detail.

(I-3-1) Rod-shaped polymerizable liquid crystal compound The rod-like polymerizable liquid crystal compound contained in the optical anisotropic layer is horizontally aligned as a monomer on a horizontal alignment film, and horizontally aligned at an air interface. A rod-shaped polymerizable liquid crystal compound. The above-mentioned "rod-like polymerizable liquid crystal compound which is horizontally aligned as a monomer on a horizontal alignment film and horizontally aligned at an air interface" means, for example, on a glass substrate which is horizontally treated on the surface, or is provided on the surface. The alignment film of the horizontal alignment induction of vinyl alcohol or the like is coated on the substrate of the horizontal alignment film, and the alignment obtained by coating the rod-shaped polymerizable liquid crystal compound as a monomer is horizontal on the alignment film and horizontally aligned at the air interface. A polymerizable liquid crystal compound.

The rod-shaped polymerizable liquid crystal compound to which the so-called homogeneous alignment property is imparted is, for example, the following formula (3), formula (4), formula (5), formula (6), formula (7) or formula (8). The compound shown.

P11-E11-B11-A11-B12-A12-B14-A14-B15-E12-P12 (3) P11-E11-B11-A11-B12-A12-B14-A14-B13-F11 (4) P11-B11- A11-B12-A12-B14-A14-B13-F11 (5) P11-E11-B11-A11-B12-A12-F11 (6) P11-B11-A11-B12-A12-B13-F11 (4) P11- E11-B11-A12-B12-A12-B13-F11 (5)

Further, in the above formulas (3), (4), (5), (6), (7), and (8), A11, A12, and A14 are independent, and each represents a divalent a cyclic hydrocarbon group, a divalent heterocyclic group, a methylene-phenylene group, an oxygen-extended phenyl group, or a sulfur-extended phenyl group. A11, A12, and A14 may also be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.

B11, B12, B13, B14, and B15 are each independently selected from -CRR'-, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S- , -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S)-,- C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N-,- N(γO)=N-, -N=N(γO)-, -C(=O)-NR-, -NR-C(=O)-, -OCH ₂ -, -NR-, -CH ₂ O -, -SCH ₂ -, -CH ₂ S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, and a group consisting of single bonds ( Further, R and R' each independently represent a divalent group of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E11 and E12 are each independently represent an olefin group having 2 to 25 carbon atoms. Further, E11 and E12 may be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. .

P11 of the formulae (4) to (8) represents a polymerizable group. P11 and P12 in the formula (3) represent a hydrogen atom or a polymerizable group, and at least one of P11 and P12 is a polymerizable group.

F11 represents a halogen atom or a hydrogen atom such as a hydrogen atom, an alkyl group, a nitroso group, a nitro group, a trifluoromethyl group or a fluorine atom.

Other liquid crystal compounds are particularly the following formulas (3-1) to (3-6), (6-1), (6-2), (8-1), and (8-2). Any one of the liquid crystal compounds shown by any one of the following formulas (3-7) to (3-12), (4-1) to (4-4), (5-1), and (5-2) ), Equation (7-1), and Equation (7-2) The liquid crystal compound shown in any of them is preferable because it is easy to obtain.

More specifically, for example, a rod-shaped polymerization contained in RMS-03-001 (trade name, manufactured by Merk Co., Ltd.) and LC-242 (trade name, manufactured by BASF Co., Ltd.) used in the examples described later. Liquid crystal compound.

In the film of the present invention, the rod-shaped polymerizable liquid crystal compound is not a rod-shaped polymerizable liquid crystal compound which has been conventionally imparted with the tilting or blending alignment property to be used, and a rod-shaped polymerizable liquid crystal which imparts the above-mentioned homogeneous alignment property is used. The compound can optionally control the tilt angle of the refractive index ellipsoid in the optical anisotropic layer. More specifically, the alignment state of the rod-shaped polymerizable liquid crystal compound can be changed by the degree of rubbing treatment of the alignment film for vertical alignment or the like. When the rod-shaped polymerizable liquid crystal compound is aligned in a liquid crystal state, the rod-shaped polymerizable liquid crystal compound changes the tilt angle of the refractive index ellipsoid in the optical anisotropic layer by the difference in tilt.

Therefore, the film of the present invention has the highest refractive index in the oblique direction with respect to the plane of the film, and can be arbitrarily changed in direction.

Further, the rod-shaped polymerizable liquid crystal compound may be polymerized in any polymerization mode. For example, a thermopolymerizable rod-shaped polymerizable liquid crystal compound or a photopolymerizable rod-shaped polymerizable liquid crystal compound may be mentioned. In the present invention, a photopolymerizable rod-like polymerizable liquid crystal compound is particularly preferable. According to this, the rod-shaped polymerizable liquid crystal compound can be polymerized at a low temperature and immobilized. Therefore, while the above-mentioned supporting substrate has a wide selection range, it is also industrially advantageous.

(I-3-2) Polymerizable Compound The polymer of the above optically anisotropic layer may be further composed of a structural unit derived from a specific polymerizable liquid crystal compound in order to impart desired wavelength dispersion characteristics of the obtained film. polymer.

The above-mentioned "specific polymerizable compound" means a group which imparts desired wavelength dispersion characteristics to the obtained film by using the above-mentioned rod-shaped polymerizable liquid crystal compound in combination.

Such a polymerizable compound is represented by the following formula (1) P2-E2-X2-B2-A2-(G2)t-Y-(G1)s-A1-B1-X1-E1-P1 (1) (wherein Y represents a base of two valences, s and t are integers each independently representing 0 or 1, and G1 and G2 are each independently represented by -CR ¹ R ² - (again, R ¹ and R ² are independent, respectively, indicating carbon a number of 1 to 4 alkyl groups, a halogen atom, or a hydrogen atom), and A1 and A2 are each independently, and represent a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group, Sulfur-extended phenyl group, A1 and A2 may also be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and B1 and B2 are each independently, and are selected from -CRR'- , -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -O- C(=O)-, -O-C(=O)-O-, -C(=S)-, -C(=S)-O-, -O-C(=S)-, -O- C(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N-, -N=N(→O)-, -C( =O)-NR-, -NR-C(=O)-, -OCH ₂ -, -NR-, -CH ₂ O-, -S CH ₂ -, -CH ₂ S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, and a group consisting of a single bond (again, R And R' is a divalent group independently representing a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X1 and X2 are each independently represented by the following formula (2) (wherein A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, and B3 represents a group selected from -CRR'-, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S) -, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N -, -N(→O)=N-, -N=N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH ₂ -, -NR- , -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, and single bond a group of the constituents (again, R and R' are each independently represent a divalent group of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a divalent group represented by an integer of 1 to 4). E1 and E2 are each independently represent an olefin group having 2 to 25 carbon atoms, and further E1 and E2 may be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. P1 and P2 are a compound represented by a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group.

Y in the above formula (1) represents a divalent group, and this group preferably has a curved structure. Here, the "bending structure" means the angle at which the bonding group of Y is bonded to the bonding group containing the group of A1 and the bonding group of Y to the group containing A2, and is formed at an angle of 100 to 140. °The structure of °. Further, the above angle is preferably from 110 to 130. When it is in the above range, the compatibility between the polymerizable compound and the rod-shaped polymerizable liquid crystal compound dissolved in the organic solution is improved. Therefore, the phase difference of the obtained film can be improved.

Specifically, the Y system can be expressed by the following formula (9). The divalent base shown and the like.

a combination of a binding group of Y, a binding group of A1, and a binding group of Y, which binds to a group containing A2, with A1, A2, C1, D1, D2, (G1)s, and (G2)t The angle formed by the base is s=t=1 in the above formula (1), and the angle can be expressed by two arrows of the following formula (9-1). Similarly, in the above formula (1), when s = t = 0, the angle can be expressed by the following formula (9-2).

In the above formula (9), C1 represents a 4-stage carbon atom or a 4-stage ruthenium atom. Among them, C1 is preferably a carbon atom of 4, because it is easy to manufacture.

In the above formula (9), D1 and D2 each represent a cyclic hydrocarbon group, a heterocyclic group, a linear hydrocarbon group having 1 to 5 carbon atoms, or a branched hydrocarbon group having 1 to 5 carbon atoms. Examples of the cyclic hydrocarbon group used in D1 and D2 include a cycloalkyl group having a carbon number of from 5 to 12 such as a cyclopentyl group or a cyclohexyl group; An aromatic group having a carbon number of about 6 to 18 or the like as shown in any of them.

Further, the heterocyclic group used in D1 and D2 may, for example, be a 5-membered ring or a 6-membered ring. The base or the like shown by either of them.

The D1 and D2 systems may also be a hydrocarbon group having 1 to 5 carbon atoms, an amine group, an ether group, a thioether group, or a single chain. Further, in D1 and D2, a hydroxyl group, an amine group, a thiol group, a cyclic hydrocarbon group, a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear chain having 1 to 5 carbon atoms may be bonded. Or a branched alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitroso group, a nitro group, or a halogen atom.

Here, the hydrocarbon group may, for example, be an olefin group such as a methylene group, an exoethyl group or a propyl group, or a linking group in which a single bond of an olefin group is substituted with a double bond or a triple bond. Further, the cyclic hydrocarbon group may be a cyclic hydrocarbon group similar to those of the users of D1 and D2. The alkyl group, the alkoxy group, and the halogen atom exemplified as the group substituted by the above A1 and A2 can be similarly exemplified.

Specific examples of the group represented by the above formula (9) include, for example, the following formulas (D-1) to (D-18). The divalent substituent shown (herein, the 4-stage atom C1 is easily produced by a carbon atom), or C1 is a carbon atom, and D1 and D2 are each a substituent of a phenyl group.

Further, a part of the hydrogen atom contained in the structure exemplified above may be an alkyl group having a carbon number of about 1 to 4 such as a methyl group, an ethyl group, an isopropyl group or a third butyl group; methoxy group; An alkoxy group having a carbon number of about 1 to 4 such as an oxy group; a trifluoromethyl group; a trifluoromethyloxy group; a nitroso group; a nitro group; and a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

Y is a carbon atom from the viewpoint of ease of production, and both D1 and D2 are preferably a substituent of a phenyl group or a substituent represented by the above formulas (D-1) to (D-12). In particular, from the viewpoint of clearly indicating the reverse wavelength dispersion, the substituents represented by the above formulas (D-1) to (D-12) are preferred.

In (G1)S and (G2)t of the above formula (1), s and t are independent, and represent an integer of 0 or 1.

In the case where s and t are 1, G1 and G2 are independently independent, and represent -CR ¹ R ² -, where R ¹ and R ² are each independently, and represent a carbon number of 1 to 4 of a methyl group, an ethyl group or the like. A halogen atom of a fluorine atom, a halogen atom, a bromine atom or the like.

Further, when s and t are 0, Y and A1 are single bonds, and Y and A2 are single bonds.

In the above formula (1), A1 and A2 are each independently represented by a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group, or a sulfur-extended phenyl group. Here, the methylene group, the ether group, and the thioether group in the methylene-phenylene group, the oxygen-extended phenyl group, or the sulfur-extended phenyl group are bonded to B1 and B2.

The divalent cyclic hydrocarbon group used in A1 and A2 may, for example, be of the following formula Any one of the aromatic groups having a carbon number of about 6 to 18, which is represented by the following formula An alicyclic group composed of a 5-member ring and a 6-member ring, and the following formula A heterocyclic group such as a 5-membered ring or a 6-membered ring represented by any of them.

Further, in the case of A1 and A2, one of the hydrogen atoms of the above-exemplified group may be an alkyl group having a carbon number of about 1 to 4 such as a methyl group, an ethyl group, an isopropyl group or a third butyl group; An alkoxy group having a carbon number of about 1 to 4 such as an oxy group or an ethoxy group; a trifluoromethyl group; a trifluoromethyloxy group; a nitroso group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; Replaced.

From the standpoint of ease of manufacture, both A1 and A2 should be of the same type. In particular, A1 and A2 are preferably a 1,4-phenylene group, a 1,4-cyclohexylene group, or a divalent group in which a carbon atom of the benzene ring is substituted by 1 to 3 nitrogen atoms, more preferably 1,4. - Stretch phenyl.

B1 and B2 are each independently selected from -CRR'-, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O) -, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S)-, -C(=S)-O -, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N -, -N=N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH ₂ -, -NR-, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, a divalent group of a group consisting of a single bond. Here, R and R' are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group, or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

From the viewpoint of ease of manufacture, both B1 and B2 are preferably the same type of divalent base.

In the above formula (1), when s and t are 0, B1 and B2 are preferably -CRR'-, -O-, -S- or NR-.

When B1 and B2 are the above-mentioned bonding group, the connection portion between A1 (A2) and B1 (B2) and the connection portion between B1 (B2) and X1 (X2) become curved, so that the angle at the connection Y can be changed. Therefore, the compatibility with the mixed rod-shaped polymerizable liquid crystal compound or the like tends to be improved, which is preferable.

In the above formula (1), when s and t are 1, it is preferred that G1 and G2 are methylene groups, and B1 and B2 are single bonds, -C≡C-, -O-C(=O). ) -O-, -O-C(=O)-, or -O-C(=O)-O- is preferred.

When B1 and B2 are the above-mentioned bonding groups, it is easy to manufacture, and since X2-B2-A2 and A1-B1-X1 in the above formula (1) are linear, respectively, it is preferable to have an orientation which tends to improve the alignment.

X1 and X2 in the above formula (1) are represented by the following formula (2) The divalent base shown.

In the above formula (2), A3 represents a divalent cyclic hydrocarbon group or a divalent heterocyclic group. Specifically, the A3 system can be similarly exemplified by the divalent cyclic hydrocarbon group and the divalent heterocyclic group exemplified in A1 and A2. From the viewpoint of ease of manufacture, a divalent group in which a carbon atom of 1,4-phenylene, 1,4-cyclohexylene or benzene ring is substituted by 1 to 3 nitrogen atoms is preferred, and 1, 4- stretched phenyl is better.

Further, from the viewpoint of easiness of production, it is preferred that both X1 and X2 are a valence group of the same type.

The B3 system can be defined in the same manner as B1. Among them, from the viewpoint of easiness of production, -OC(=O)-, -C(=O)-O-, -O-, or a single bond is preferred.

n represents an integer from 1 to 4. When n is 2 or more, the structural units composed of A3 and B3 may be different from each other as in the compounds (1-2) to (1-4) in Table 1 to be described later.

When the composition containing the obtained polymerizable compound is cast, n is preferably 1 or 2 from the viewpoint of easy handling. Further, n is preferably 1 from the viewpoint of easiness of manufacture.

E1 and E2 are each independently, and represent an olefin group having 2 to 25 carbon atoms, preferably an olefin group having 4 to 10 carbon atoms.

The hydrogen atom of E1 and E2 may be substituted by an alkyl group, an alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitroso group, a nitro group or a halogen atom, but a hydrogen atom is preferred. .

When both E1 and E2 are the same type of olefin group, they are preferred because they are easy to manufacture.

P1 and P2 represent a hydrogen atom or a polymerizable group.

In the present specification, the term "polymerizable group" means a substituent which can polymerize a polymerizable compound and the above-mentioned rod-shaped polymerizable liquid crystal compound. Specifically, for example, a vinyl group, a stilbene group, a propylene group, a methacryl group, a carboxyl group, a methylcarbonyl group, a hydroxyl group, a decylamino group, an alkylamino group having 1 to 4 carbon atoms, an amine group, An epoxy group, an oxobutane group, an aldehyde group, an isocyanate group, a sulfur isocyanate group or the like.

Further, the polymerizable group may contain a group exemplified by B1 or B2 in order to connect the above-exemplified group with E1 or E2.

Among them, an acryl fluorenyl group or a methacryl fluorenyl group is preferred, and an acryl fluorenyl group is more preferred. When such a base is used, it is easy to manufacture except that the treatment at the time of photopolymerization is easy.

It is preferable that at least one of P1 and P2 has a polymerizable group, and any of P1 and P2 is a polymerizable group. Thereby, the film hardness of the obtained film can be made good.

Specific examples of the polymerizable compound include compounds represented by Tables 1 to 4 and the like.

In the above optically anisotropic layer, any of the above polymerizable compounds may be contained alone, but a plurality of different polymerizable compounds may be contained. Among them, the compounds described in Tables 1 and 2 are preferred. When such a compound is used, the film system of the present invention can clearly represent reverse wavelength dispersion. Further, it is more preferred to contain the compound described in Table 1. If such a compound is used, the film of the present invention can be easily produced.

Here, the expression of the table is described by taking the compound (1-1) as an example. The phrase "A1=A2" means that A1 and A2 are the same stretching phenyl groups. "B1 = A side of B2" means that the ether moiety of the ester group is bonded to A (phenylene). Further, "B1 = X side of B2" indicates that the carbonyl moiety of the ester group is bonded to X (phenylene ether group). Further, when there is no designated side, it means that it can be replaced in the direction of either one.

The polymerizable compound is preferably a compound described in Table 1 or Table 2, and the compound described in Table 1 is more preferable, and it is preferable to use the following formula (1-1), (1-2), (1-3), (1). -4), (1-5), (1-11), (1-45), (1-49), and (1-50).

In the method of producing the polymerizable compound of the above formula (1), the s=t=0 in the above formula (1), for example, the corresponding carbonyl compound is used as the C1, D1 and D2. The structure of the compound is a method in which a halide containing a compound of A1 (A2), B1 (B2), X1 (X2), E1 (E2), and P1 (P2) is subjected to dehydration condensation. A compound containing A1 (A2), B1 (B2), X1 (X2), E1 (E2), and P1 (P2) can be made to contain A1 (=A2), B1 (=B2), and X1 (=X2). The compounds of each structural unit of E1 (=E2) and P1 (=P2) are dehydration condensation reaction, esterification reaction, Williamson reaction, Ullmann reaction, benzylation reaction, bacterial head reaction, Suzuki Gongpu reaction, root bank reaction, It is produced by combining a bear field reaction, a Laoshan reaction, a Buchwald-Hartwig reaction, a Wittig reaction, a Friedel craft reaction, a Heck reaction, or an aldehyde reaction.

A method for producing a polymerizable compound in which the s and t in the above formula (1) are 1 and G1 and G2 are all a methylene chain, as in the case of the compound represented by the above formula (1-2), for example, A compound in which a structural unit of C2 and A1 (C3 and A2) is added to the carbonyl compound, and a halogenated benzyl group having an iodine in a benzene ring is reacted with an alkali metal hydroxide to synthesize A1 (A2), C1, and G1. A method of reacting a compound of (G2), D1 and D2 with a separately synthesized compound containing B1 (B2), X1 (X2), E1 (E2) and P1 (P2); and A1 obtained from the same procedure A compound of A2, C1, G1, G2, D1 and D2, a method of sequentially reacting a compound having a structure of B1 (B2), X1 (X2), E1 (E2), and P1 (P2).

The wavelength dispersion characteristics of the obtained film are determined by the ratio of the structural unit derived from the rod-shaped polymerizable liquid crystal compound and the polymerizable compound. In the case where the above polymerizable compound is not contained in the present invention, the obtained film is a film which exhibits a positive wavelength dispersion. Further, by increasing the content of the structural unit derived from the above polymerizable compound, the dispersion from the positive wavelength to the reverse wavelength dispersion and the wavelength dispersion property can be arbitrarily adjusted. Therefore, the film of the present invention is preferably one containing the above-mentioned polymerizable compound in an amount which can obtain only the desired wavelength dispersion characteristics. The content of the above polymerizable compound required to impart the desired wavelength dispersion property can be determined in the following manner. For example, the ratio of the structural unit derived from the polymerizable compound contained in the composition containing the rod-shaped polymerizable liquid crystal compound and the polymerizable compound is adjusted to determine the phase difference value of the obtained film. From the result, the content of the structural unit derived from the polymerizable compound can be determined.

(I-3-3) The other constituent compound [polymerization initiator] may further contain a polymerization initiator for polymerizing the rod-shaped polymerizable liquid crystal compound or the polymerizable compound in the optical anisotropic layer. The polymerization initiator is not particularly limited as long as it can polymerize the above compound. In a preferred embodiment of the film of the present invention, the rod-like polymerizable liquid crystal compound is preferably photopolymerized. Therefore, the above polymerization initiator is preferably a photopolymerization initiator.

The photopolymerization initiator may, for example, be a benzoin, a benzophenone, a benzyl acetal, an α-hydroxy ketone, an α-amino ketone, an iodonium salt or a sulfonium salt. More specifically, for example, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 250, and Irgacure 369 (above, all manufactured by Chiba Specialty Chemicals Co., Ltd.), Seikuol BZ, Seikuol Z, and Seikuol BEE (all of which are Seiko Chemical Co., Ltd.) )), Kayacure BP 100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Co., Ltd.), Adekaoptomer-SP-152, Adeka optomer-SP-170 (all, all of which are Asahi Kasei).

The rod-shaped polymerizable liquid crystal compound and the polymerizable compound can be photopolymerized by using such a photopolymerization initiator. In addition, the content of the polymerization initiator is preferably 10% by weight or less based on the composition of the liquid crystal compound to be described later, so that the alignment property of the rod-like polymerizable liquid crystal compound is not disturbed.

[Polymerization Inhibitor] Further, a polymerization inhibitor may be contained in the above optically anisotropic layer. The polymerization inhibitor is not particularly limited, and examples thereof include a hydroquinone having a substituent such as hydroquinone or an alkyl ether, and a substituent catechol such as an alkyl ether such as butyl catechol, and benzene. A radical scavenger such as a trisphenol or a 2,2,6,6-tetramethyl-1-pyrazine oxygen radical, a thiophenol, a β-naphthylamine, and a β-naphthol.

By using the polymerization inhibitor described above, polymerization of the rod-shaped polymerizable liquid crystal compound or the polymerizable compound can be controlled, and the stability of the optical anisotropic layer can be improved.

[Photosensitizer] The optical anisotropic layer may further contain a photosensitizer. The photosensitizer is not particularly limited, and examples thereof include xanthone such as xanthone or thioxanthone, anthracene, an anthracene having a substituent such as an alkyl ether, and phenolphthalein, and Rubrene.

By using the photo sensitizer, the polymerization of the rod-shaped polymerizable liquid crystal compound or the polymerizable compound can be made highly sensitive.

[Coating Agent] Further, a coating agent may be contained in the optical anisotropic layer. The above-mentioned leveling agent is not particularly limited, and a conventionally known leveling agent can be added. The above-mentioned leveling agent may, for example, be an additive for radiation hardening paint (BYK Chemie Japan; BYK-352, BYK-353, BYK-361N), a coating additive (manufactured by Toray Dow Corning: SH28PA, DC11PA, ST80PA), and Coating additive (manufactured by Shin-Etsu Silicone: KP321, KP323, X22-161A, KF6001).

The optical anisotropic layer can be smoothed by using the above-mentioned leveling agent. Further, in the production process of the film, the fluidity of the composition containing the liquid crystal compound described later can be controlled, or the crosslinking density of the rod-shaped polymerizable liquid crystal compound or the polymerizable compound can be adjusted.

<II. Method for Producing Related Film of the Present Invention>

The method for producing a film of the present invention can be suitably used for producing the film of the present invention described above. Specifically, the method includes the following steps: (A) a step of applying a composition containing the rod-like polymerizable liquid crystal compound to the alignment film for vertical alignment (hereinafter also referred to as "coating step of a composition containing a liquid crystal compound") And (B) a heating step of heating the coating film formed by the coating step of the composition containing the liquid crystal compound at 25 to 120 ° C for 10 seconds to 60 minutes (hereinafter also referred to as "the composition containing the liquid crystal compound" Heating step").

According to the above configuration, since the rod-shaped polymerizable liquid crystal compound is in an unpolymerized state, the obtained film becomes an unpolymerized film. Further, the rod-shaped polymerizable liquid crystal compound can be mixed or obliquely aligned with respect to the plane of the film on the rubbing-treated vertical alignment film. Therefore, according to the above configuration, an unpolymerized film having the highest refractive index in the oblique direction with respect to the film plane can be produced. In the method for producing a film of the present invention, a method for producing such an unpolymerized film may be contained.

The alignment film for vertical alignment and the rod-shaped polymerizable liquid crystal compound can be similarly used in the film "I, the film of the present invention". In the optical anisotropic layer formed by the above steps, the rod-shaped polymerizable liquid crystal compound is obliquely aligned with respect to the alignment film for vertical alignment. Therefore, it is possible to manufacture a film whose refractive index changes in an oblique direction with respect to the plane of the film. Further, in the method for producing a film according to the present invention, the degree of rubbing treatment in the alignment film for vertical alignment is changed, and the tilt angle of the refractive index ellipsoid in the optical anisotropic layer can be arbitrarily controlled. Therefore, various films of various inclination angles can be easily manufactured.

Further, the method for producing a film of the present invention may further comprise (C) a heating step of the composition containing the liquid crystal compound, in addition to the step of coating the composition containing the liquid crystal compound and the step of heating the composition containing the liquid crystal compound. a step of polymerizing (crosslinking) the unpolymerized film (hereinafter also referred to as "liquid crystal compound polymerization step") or (D) a step of rubbing the alignment film for vertical alignment (hereinafter also referred to as "friction step"), E) a composition comprising a rod-shaped polymerizable liquid crystal compound (hereinafter, also referred to as "a composition preparation step containing a liquid crystal compound") applied to an alignment film for a vertical alignment, and (F) a support substrate The step of forming an alignment film for vertical alignment (hereinafter also referred to as "alignment film formation step for vertical alignment"). These four steps may also be all contained, or may contain only one or two. Of course, it does not contain either.

Hereinafter, the step of forming the alignment film for vertical alignment, the rubbing step, the step of preparing the composition containing the liquid crystal compound, the step of coating the composition containing the liquid crystal compound, the step of heating the composition containing the liquid crystal compound, and the step of polymerizing the liquid crystal compound will be described in detail.

(II-1) Step of forming an alignment film for vertical alignment

In the above-described alignment film forming step for vertical alignment, an alignment film for vertical alignment is formed on the support substrate. The support substrate is not particularly limited. For example, a support substrate exemplified in <1. The film of the present invention> can be used. The alignment film for the vertical alignment is not particularly limited, and for example, an alignment film for a vertical alignment exemplified in <I. The film of the present invention> can be used. When such an alignment film for vertical alignment is used, since the refractive index is not required to be extended, the in-plane unevenness of the birefringence becomes small. Therefore, it is possible to provide an effect of an optical film which can correspond to the enlargement of the FPD on the support substrate.

The method of forming the alignment film for vertical alignment on the above-mentioned support substrate is not particularly limited, and a conventionally known method can be used. For example, a material for the vertical alignment alignment film is coated on the support substrate, and then, by tempering, an alignment film for vertical alignment can be formed on the support substrate.

The thickness of the alignment film for vertical alignment obtained in this manner is not particularly limited, but is preferably from 10 nm to 10,000 nm, more preferably from 10 nm to 1000 nm. In the above range, in the optical anisotropic layer forming step to be described later, the rod-shaped polymerizable liquid crystal compound can exhibit a desired angular alignment on the alignment film for vertical alignment.

(II-2) Friction step

In the rubbing step, the vertical alignment alignment film obtained in the above-described vertical alignment alignment film forming step is subjected to a rubbing treatment. Thereby, in the heating step of the composition containing the liquid crystal compound to be described later, the rod-shaped polymerizable liquid crystal compound can be directly aligned horizontally at the interface of the air layer, and the alignment film interface at the vertical alignment can be obliquely aligned. In addition, the alignment film for vertical alignment may not be obtained in the step of forming the alignment film for vertical alignment, or may be an alignment film for vertical alignment having equivalent physical properties, and may be used as another product, for example, a commercially available product.

The method of rubbing the alignment film for vertical alignment is not particularly limited, and a conventionally known method can be used. For example, a method of winding up the rubbing cloth, placing the rotating rubbing roller on the table, and contacting the transferred alignment film for the vertical alignment can be used.

The rubbing cloth is not particularly limited as long as it can be wound around a rubbing roll. The material of the rubbing cloth may, for example, be various materials such as enamel, cotton cloth, wool, and silk. Moreover, the same material can be used, and the thickness or length of the wire can be changed to change the friction state. In order to uniformly form the friction state, the thickness or length of the wire is preferably uniform.

The diameter of the above-mentioned rubbing roller is generally controlled to stably control its rotation, preferably from 10 nm to 300 nm in diameter. Further, by changing the diameter of the rubbing roller, the angle or area of contact with the alignment film can be adjusted.

Further, the number of rotations of the friction roller is determined by the diameter of the friction roller. However, in order to stably rotate the friction roller, it is preferably 100 to 2000 rpm. Further, even by changing the number of rotations of the above-described friction roller, the application of friction can be adjusted.

The table speed of the above-mentioned table and the conveying speed of the alignment film for the vertical alignment are generally too slow for the conveying speed of the alignment film for the vertical alignment, and it is difficult to carry it stably when it is too fast, so it is preferable to dig at 0.1 m/min. 10m/min. Further, by changing the conveying speed of the table speed and the alignment film for the vertical alignment, the application of the friction can be adjusted.

Further, in the above-described friction method, the amount of extrusion and the contact length are not particularly limited, and the length of the wire of the rubbing cloth may be set so that the desired friction effect can be obtained. In addition, the above-mentioned "squeezing amount" means the amount by which the rubbing roller is pressed against the alignment film for the vertical alignment, and is expressed by the length of the hair of the rubbing cloth pressed against the alignment film. In the above friction method, it can be abutted to the extent that the cloth of the rubbing cloth is exposed only in the vertical direction. Moreover, the "contact length" means the length in which the rubbing roller is in contact with the substrate. The contact long friction roller is in contact with the vertical alignment alignment film, and when the friction roller is completely pressed, the length of contact between the friction roller and the alignment film for vertical alignment can be changed.

In the above-described rubbing step, the vertical alignment alignment film is rubbed by the method as exemplified above, but the number of rubbing of the vertical alignment alignment film in the rubbing step is not particularly limited. That is, in the rubbing step, the alignment film for the vertical alignment may be rubbed only once, or the control alignment rubbing treatment may be performed plural times.

(II-3) Modulation step containing a liquid crystal compound composition

In the step of preparing a composition containing a liquid crystal compound, a composition containing a rod-like polymerizable liquid crystal compound is prepared. Specifically, a solution in which the rod-shaped polymerizable liquid crystal compound is dissolved in an organic solvent is prepared. The rod-like polymerizable compound may be a rod-like polymerizable liquid crystal compound as described in <I. The film of the invention>. In addition, the organic solvent is not particularly limited as long as it can dissolve the rod-shaped polymerizable liquid crystal compound. For example, cyclopentanone, cyclohexanone, methyl ethyl ketone, toluene, ethyl acetate, methyl cellosolve, butyl cellosolve, isopropyl alcohol, methyl amyl ketone, xylene, acetonitrile, tetrahydrofuran, γ-butyl Lactone, dimethoxyethane, ethyl lactate, chloroform, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. These organic solvents may be used singly or in combination of plural kinds.

Further, the concentration of the rod-shaped polymerizable liquid crystal compound in the above composition is not particularly limited, and if the concentration is too low, the optical anisotropic layer is too thin, and optical anisotropy required for optical compensation of the liquid crystal panel cannot be obtained. Sexual tendency. On the other hand, if the concentration is too high, the viscosity of the solution containing the composition of the liquid crystal compound tends to be too high, and the coating film thickness tends to be uneven. Therefore, the above concentration is preferably from 5 to 50% by weight. If it is within the above range, it does not cause the above problems.

Further, the above composition may further contain a plurality of liquid crystal compounds different from the specific polymerizable compound and/or the rod-shaped polymerizable liquid crystal compound.

The liquid crystal compound may be any other liquid crystal compound as described in <I. The film of the present invention>.

The content of the liquid crystal compound may be appropriately determined in accordance with the phase difference value obtained by the obtained film. Specifically, the ratio of the structural unit derived from the liquid crystal compound contained in the above composition is adjusted by imparting the desired phase difference value, and the phase difference value of the obtained optical film is obtained. Based on this result, the content of the structural unit derived from the above liquid crystal compound can be determined.

Generally, the phase difference can be controlled by changing the film thickness. However, even if the film thickness control can arbitrarily control the phase difference in the normal direction, it is difficult to control the phase difference when the incident angle is changed, and it is necessary to change the chemical structure of the above-mentioned rod-shaped polymerizable liquid crystal compound. Further, by adding the structural unit derived from the above liquid crystal compound, not only the phase difference value in the normal direction but also the phase difference value of all angles can be arbitrarily adjusted. In other words, the shape of the refractive index ellipsoid which the optical anisotropic layer has can be arbitrarily controlled by adding a structural unit derived from the above liquid crystal compound. However, in the case where too many structural units derived from the above liquid crystal compound are added, the vertical alignment of the present invention may not be obtained. Therefore, for example, the content of the structural unit derived from the liquid crystal compound is 5 to 50 parts by weight based on 100 parts by weight of the total of the structural unit derived from the above liquid crystal compound and the structural unit derived from the rod-shaped polymerizable liquid crystal compound. By forming the above content, the shape of the refractive index ellipsoid of the obtained film can be arbitrarily controlled.

The polymerizable compound may be a polymerizable compound described in <I. The film of the present invention>. By containing such a polymerizable compound in the above composition, a film having an arbitrary wavelength dispersion property can be produced.

The content of the polymerizable compound may be appropriately determined in accordance with the wavelength dispersion characteristics obtained by the obtained film. Specifically, the ratio of the structural unit derived from the liquid crystal compound contained in the above composition is adjusted by imparting the desired wavelength dispersion characteristic, and the phase difference value of the obtained optical film is obtained. Based on this result, the content of the structural unit derived from the above liquid crystal compound can be determined.

In general, the absence of the above-mentioned polymerizable compound or a film containing only a small amount means a positive wavelength dispersion. Further, by increasing the content of the structural unit derived from the above polymerizable compound, the wavelength dispersion characteristics of the positive wavelength dispersion to the reverse wavelength band can be arbitrarily adjusted. When a film which exhibits a reverse wavelength dispersion is obtained, for example, a structural unit derived from a polymerizable compound is preferably used in an amount of 100 parts by weight based on 100 parts by weight of the total of the structural unit derived from the polymerizable compound and the structural unit derived from the rod-shaped polymerizable liquid crystal compound. The content is 5 to 50 parts by weight. By forming the above content, a film which exhibits a large phase difference can be formed simultaneously with the display of the reverse wavelength dispersion.

Further, in the method for producing a film of the present invention, the wavelength dispersion characteristics (positive wavelength dispersion to reverse wavelength dispersion) of the obtained film are changed by the composition of the composition. Therefore, the effect of the wavelength dispersion characteristics of the film can be arbitrarily adjusted in a very simple manner.

Further, the above composition may further contain a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and the like.

As the above polymerization initiator, a polymerization initiator described in <I. Film of the Invention> can be used. In addition, the amount of the polymerization initiator to be added is preferably an amount suitable for the polymerization reaction of the rod-shaped polymerizable liquid crystal compound and/or the polymerizable compound, as long as the alignment property of the rod-shaped polymerizable liquid crystal compound is not disturbed. In other words, it is preferable to appropriately determine the type of the rod-like polymerizable liquid crystal compound, the polymerizable compound, and the polymerization initiator, and the composition of the above composition. The specific value of the amount of the polymerization initiator to be added is not particularly limited. For example, it is preferably from 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the rod-like polymerizable liquid crystal compound, and from 0.5 part by weight to 10 parts by weight. Better. When it is in the above range, the rod-like polymerizable liquid crystal compound can be polymerized without disturbing the alignment property of the rod-like polymerizable liquid crystal compound.

The polymerization inhibitor described above can be used as the polymerization inhibitor described in <I. Film of the Invention>. In addition, the amount of the polymerization inhibitor to be added is not particularly limited, and the polymerization of the rod-shaped polymerizable liquid crystal compound and/or the polymerizable compound can be adjusted without confusing the alignment property of the rod-like polymerizable liquid crystal compound. It is sufficient to increase the stability of the optical anisotropic layer. Specifically, it is preferably from 0.1 part by weight to 30 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the rod-like polymerizable liquid crystal compound. When it is in the above range, the alignment of the rod-like polymerizable liquid crystal compound is not disturbed, and the polymerization of the rod-shaped polymerizable liquid crystal compound can be controlled, and the stability of the optical anisotropic layer can be improved.

As the photosensitizing agent, a photo sensitizer described in <I. The film of the present invention> can be used. In addition, the amount of the light sensitizer added is not particularly limited, and the polymerization of the rod-shaped polymerizable liquid crystal compound and/or the polymerizable compound can be made highly sensitive as long as the alignment property of the rod-like polymerizable liquid crystal compound is not disturbed. The amount can be reduced. Specifically, it is preferably from 0.1 part by weight to 30 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the rod-like polymerizable liquid crystal compound. When it is in the above range, the alignment of the rod-like polymerizable liquid crystal compound is not disturbed, and the polymerization of the rod-shaped polymerizable liquid crystal compound can be improved.

As the above-mentioned leveling agent, the leveling agent described in <I. Film of the Invention> can be used. Further, the amount of the above-mentioned leveling agent to be added is not particularly limited, and the optically anisotropic layer can be smoothed or the composition containing the liquid crystal compound can be controlled to be coated, as long as the alignment property of the rod-like polymerizable liquid crystal compound is not disturbed. The fluidity at the time or the amount of crosslinking density of the rod-shaped polymerizable liquid crystal compound may be adjusted. Specifically, it is preferably from 0.1 part by weight to 30 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the rod-like polymerizable liquid crystal compound. When the alignment property of the rod-like polymerizable liquid crystal compound is not disturbed within the above range, the optical anisotropic layer can be smoothed, or the fluidity at the time of coating of the liquid crystal-containing composition can be controlled, or the rod-shaped polymerizable liquid crystal can be adjusted. Crosslink density of the compound.

(II-4) Coating step containing a liquid crystal compound composition

In the coating step containing the liquid crystal compound composition, the composition prepared by the above-described preparation step containing the liquid crystal compound composition is applied onto the alignment film for vertical alignment. Thereby, a coating film containing the above composition can be formed on the alignment film for vertical alignment. Here, the composition is not a composition prepared by a preparation step of a liquid crystal compound composition, but a composition having an equivalent composition, and may also contain a composition of a separately prepared rod-shaped polymerizable liquid crystal compound, for example, a city. Sale.

The method of applying the above composition to the alignment film for vertical alignment is not particularly limited, and a conventionally known method can be used. For example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, a die coating method, a dip coating method, a rod coating method, a spin coating method, and the like can be given.

Further, the coating amount of the above composition is not particularly limited, and may be applied in an appropriate amount so as to impart a film thickness of a desired phase difference to the obtained film. As described above, by adjusting the film thickness, the phase difference (delay value, Re (λ)) of the obtained film can be determined.

The thickness of the layer formed by applying the above composition is as described above, and is different depending on the phase difference of the obtained film. In the present invention, the above thickness is preferably from 0.1 to 10 μm, more preferably from 0.5 to 2 μm. If it is within the above range, the phase difference value of the above-mentioned film of the present invention can be formed.

As described above, in the coating step containing the liquid crystal compound composition, an optical anisotropic layer (liquid crystal layer) is laminated on the alignment film for vertical alignment laminated on any of the support substrates. Therefore, the production of the liquid crystal cell can reduce the production cost as compared with the method of injecting the liquid crystal compound into the liquid crystal cell. It is also possible to produce a film on a roll film.

(II-5) Heating step containing a liquid crystal compound composition

In the heating step of the liquid crystal compound-containing composition, the coating film formed by the coating step containing the liquid crystal compound composition is heated. Thereby, the unpolymerized film in which the solvent contained in the coating film is dried and the rod-shaped polymerizable liquid crystal compound is in an unpolymerized state can be obtained. In the present invention, the unpolymerized film thus obtained may also be contained. The above unpolymerized film means a nematic liquid crystal phase having a birefringence obtained by alignment in a single region. Further, the above unpolymerized film is usually at a low temperature of from about 10 to 120 ° C, preferably from 25 to 80 ° C. Therefore, in the present invention, a substrate having low heat resistance can be used as the above-mentioned support substrate.

In the heating step of the liquid crystal compound-containing composition, the method of heating the composition, the heating conditions, and the like may be carried out as long as the unpolymerized film having the above physical properties can be obtained. Specifically, the heating temperature is preferably from 10 to 120 ° C, more preferably from 25 to 80 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. When the heating temperature and the heating time are within the above range, a support substrate which is not sufficiently heat resistant may be used as the support substrate.

(II-6) Liquid crystal compound polymerization step

In the liquid crystal compound polymerization step, the unpolymerized film obtained by the heating step containing the liquid crystal compound composition described above is polymerized and cured. Thereby, the film in which the alignment property of the rod-shaped polymerizable liquid crystal compound is immobilized is obtained, that is, it becomes a polymer film. Therefore, it is possible to manufacture a polymer film having the highest refractive index in the oblique direction with respect to the plane of the film.

The method of polymerizing the unpolymerized film can be determined depending on the type of the rod-shaped polymerizable liquid crystal compound and the polymerizable compound. For example, the above unpolymerized film can be polymerized by photopolymerization or thermal polymerization. In the present invention, it is particularly preferred to polymerize the unpolymerized film by photopolymerization. According to this, since the unpolymerized film can be polymerized at a low temperature, the heat-resistant property of the support substrate can be selected in a wide range. Moreover, it is easy to manufacture in industry.

The method of photopolymerizing the unpolymerized film is not particularly limited, and a conventionally known method can be used. For example, the unpolymerized film can be polymerized by irradiating the unpolymerized film with ultraviolet rays.

As described above, in the method for producing a film according to the present invention, a liquid crystal polymer is not used as the liquid crystal compound. Further, the rod-shaped polymerizable liquid crystal compound can be crosslinked by photopolymerization. Therefore, it is possible to exert an effect that is not susceptible to the influence of the birefringence caused by heat. Further, in the alignment film for vertical alignment, a surface treatment agent such as a surfactant may not be used. In other words, the alignment film (orthogonal alignment film) of the film of the present invention is easy to produce a film because the adhesion between the support substrate and the alignment film and the adhesion between the alignment film and the optical anisotropic layer are good. . Further, according to the method for producing a film of the present invention, an optical compensation film having a desired retardation value in the film can be produced as compared with those expected to have the same performance in the stretched film.

<III. Utilization of the relevant film of the present invention>

The film of the present invention can be widely used as an optical film having excellent wavelength dispersion characteristics. The optical film may, for example, be an antireflection film such as an antireflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, or an optical compensation film for viewing angle compensation of a transmissive liquid crystal display.

Further, the film of the present invention can be used for a phase difference plate including a reflective liquid crystal display and an organic electroluminescence (EL) display, and a flat display device of the retardation film or the optical film. The flat display device is not particularly limited, and examples thereof include a liquid crystal display (LCD) or an organic electroluminescence (EL).

Thus, the film of the present invention can be considered for a wide range of uses. For example, a polarizing film comprising a film of the present invention and a flat display device having the film or the polarizing film of the present invention will be described below.

(III-1) Polarizing film

The embodiment of the polarizing film of the present invention is as follows according to the third to third embodiments, but the polarizing film of the present invention is not limited thereto.

The polarizing film of the present invention is a film having a polarizing function, that is, a film obtained by laminating one side or both sides of a polarizing layer directly or by using an adhesive.

For example, as shown in FIGS. 3A to 3E, (1) the film 1 and the polarizing layer 2 are directly bonded together (FIG. 3A); (2) the film 1 and the polarizing layer 2 are An embodiment in which the adhesive layer or the adhesive layer 3 is bonded (Fig. 3B); (3) an embodiment in which the film 1 and the film 1' are directly bonded together, and the film 1' and the polarizing layer 2' are directly bonded together. (3C); (4) an embodiment in which the film 1 and the film 1' are bonded together via the adhesive layer or the adhesive layer 3, and the polarizing layer 2 is directly bonded to the film 1' (Fig. 3D), and (5) An embodiment (Fig. 3E) in which the film 1' and the film 1' are bonded to each other via the adhesive layer or the adhesive layer 3, and the film 1' and the polarizing layer 2 are bonded together via the adhesive layer 3'.

For the convenience of explanation, the same elements (components) are given the same reference numerals.

In the 3F drawing, the liquid crystal layer 11 is used as the film 1, and the film 1 does not contain the alignment layer 12. The film 1 and the polarizing layer 2 are bonded together via a pair of adhesive layers or adhesive layers 3.

In the 3GG, the liquid crystal layer 11 can be used as the film 1, and the film 1 may not include the alignment layer 12. The pair of films 1 are bonded to each other via the adhesive layer or the adhesive layer 3, and further, the polarizing layer 2 is bonded to the outside via a pair of adhesive layers or adhesive layers 3.

The 3H figure shows the same structure as the 3F figure. However, unlike the FIG. 3F, a laminated structure including a support film 13 and an alignment film 12 formed on the surface of the support film 13 and the alignment film 12 may be used as the film 1A. The liquid crystal layer 11 formed on the surface.

Fig. 3I has the same structure as Fig. 3G. However, in the third embodiment, a laminate is used as the film 1A, and the film 1A is an alignment film 12 including the support film 13 formed on the surface of the support film 13, and a liquid crystal formed on the surface of the alignment film 12. The layered body of layer 11.

3J and 3K show the same structure as the 3G. However, one of the two films is a liquid crystal layer 11 as the film 1, and the other is a laminate 1A containing the support film 13 and the alignment film 12 formed on the surface of the support film 13. And a liquid crystal layer 11 formed on the surface of the alignment film 12.

The polarizing layer 2 is not particularly limited as long as it is a film having a polarizing function. For example, the polarizing layer 2 may be a film in which a polyvinyl alcohol-based film is adsorbed by adsorbing iodine or a dichroic dye, or a film in which a polyvinyl alcohol-based film is stretched to adsorb iodine or a dichroic dye.

The adhesive used for the adhesive layer 3 and the adhesive layer 3' is not particularly limited, but an adhesive having high transparency and excellent heat resistance is preferred. As such an adhesive, for example, an acrylic, epoxy or polyurethane adhesive can be used.

Further, in the above polarizing film, as shown in Figs. 3C to 3E, the film of the present invention may be bonded to one to three layers as needed.

(III-2) Flat display device

The flat display device of the present invention is provided with a film or a polarizing film according to the present invention. For example, a liquid crystal display device including the polarizing film of the present invention and a liquid crystal panel bonded to the liquid crystal panel, or the organic electroluminescence provided with the polarizing film of the present invention and the light-emitting layer (hereinafter also referred to as "EL" panel organic EL display device.

In the embodiment of the flat display device according to the present invention, the liquid crystal display device and the organic EL will be described in detail below, but the present invention is not limited thereto.

[Embodiment 1]

The liquid crystal display device of the first embodiment includes the liquid crystal panel shown in Fig. 4 . The liquid crystal panel is formed by bonding the polarizing film 4 and the liquid crystal panel 6 via the adhesive layer or the adhesive layer 5. According to the above configuration, an electrode (not shown) is used, and a voltage is applied to the liquid crystal panel to drive the liquid crystal molecules to exhibit a light blocking effect.

[Form 2]

The organic EL display device of the second aspect of the invention includes the organic EL panel shown in FIG. The organic EL panel is formed by bonding the polarizing film 4 and the light-emitting layer 7 via the adhesive layer or the adhesive layer 5.

In the above organic EL panel, the polarizing film 4 functions as a wide-band circular polarizing plate. Further, the light-emitting layer is a layer of at least one layer composed of a conductive organic compound.

Further, the present invention is not limited to the above-described respective configurations, and various modifications can be made in the scope of the claims, and the embodiments obtained by the respective technical methods disclosed in the different embodiments can be appropriately combined. It is included in the technical scope of the present invention.

[Examples]

The present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited thereto. A person skilled in the art can make various changes, modifications, and alterations without departing from the scope of the invention. Further, the wavelength dispersion characteristics in the following examples and comparative examples were carried out as follows.

[Measurement of Wavelength Dispersion Characteristics]

The incident angle dependence of the phase difference of the produced film was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.) at a wavelength of 585.6 nm. At the same time, the manufactured front phase difference value R ₀ (nm) was measured using a measuring machine (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.) at a wavelength of 585.6 nm.

[Example 1: Production of film]

A polyimide film for vertical alignment (SE-5300, manufactured by Nissan Chemical Co., Ltd.) was applied to a glass substrate, and then tempered to obtain a film having a thickness of 104 nm. Then, the alignment film shown in Table 6 was rubbed once with 嫘萦 (Yoshigawa Chemical Co., Ltd. YA-20-R), and then the coating liquid of the composition of Table 5 was applied by spin coating, and dried at 55 ° C for 1 minute. . The obtained unpolymerized film was confirmed to be a single region by a polarizing microscope. Then, the polymerizable liquid crystal compound was polymerized by irradiation with ultraviolet rays to produce a film having a film thickness of 0.9 μm. The obtained film had no elasticity and was uniformly applied, and even if it was left indoors for 30 days, peeling was not observed, the adhesion was good, and the optical characteristics were not changed.

Regarding the obtained film, the incident angle dependency was measured by the above method. The inclination angle of the refractive index ellipsoid of the obtained optical anisotropy layer is shown in Table 6.

With respect to the obtained film, the front phase difference value R _{0 was} also measured by the above method, and the results are shown in Table 6.

[Examples 8 to 11: Fabrication of Film]

A polyimide film for vertical alignment (SE-5300, manufactured by Nissan Chemical Co., Ltd.) was applied to a glass substrate, and then tempered to obtain a film having a thickness of 104 nm. Then, the alignment film shown in Table 8 was rubbed once with 嫘萦 (Yoshikawa Chemical Co., Ltd. YA-20-R), and then the coating liquid of the composition of Table 7 was applied by spin coating, and dried at 55 ° C for 1 minute. . The obtained unpolymerized film was confirmed to be a single region by a polarizing microscope. Then, the polymerizable liquid crystal compound was polymerized by irradiation with ultraviolet rays to produce a film having a film thickness of 0.9 μm. The obtained film had no elasticity and was uniformly applied, and even if it was left indoors for 30 days, peeling was not observed, the adhesion was good, and no change in optical characteristics was observed.

With respect to the obtained optical film, the incident angle dependency was measured by the above method. The inclination angle of the refractive index ellipsoid of the obtained optical anisotropy layer is shown in Table 8. With respect to the obtained optical film, the front retardation value R _{0 was} also measured by the above method, and the results are shown in Table 8.

[Comparative Examples 1 to 2: Fabrication of Thin Films]

After coating a polyvinyl alcohol aqueous solution on the glass substrate, it was tempered to obtain a film having a thickness of 100 nm. Then, the alignment film shown in Table 9 was rubbed once with 嫘萦 (Yoshikawa Chemical Co., Ltd. YA-20-R), and then the coating liquid of the composition of Table 5 was applied by spin coating, and dried at 55 ° C for 1 minute. . The obtained unpolymerized film was confirmed to be a single region by a polarizing microscope. Then, the polymerizable liquid crystal compound was polymerized by irradiation with ultraviolet rays to produce a film having a film thickness of 0.9 μm. The obtained film had no elasticity and was uniformly applied, and even if it was left indoors for 30 days, peeling was not observed, the adhesion was good, and no change in optical characteristics was observed.

With respect to the obtained optical film, the incident angle dependency was measured by the above method. The inclination angle of the refractive index ellipsoid of the obtained optical anisotropy layer is shown in Table 9.

With respect to the obtained film, the front surface difference value R _{0 was} measured by the above method, and the results are shown in Table 9.

[Comparative Example 3: Manufacturing of film]

After coating a polyvinyl alcohol aqueous solution on the glass substrate, it was tempered to obtain a film having a thickness of 100 nm. This alignment film was subjected to rubbing treatment as shown in Table 10 once by yttrium (YA-20-R manufactured by Yoshikawa Chemical Co., Ltd.), and then the coating liquid of the composition of Table 7 was applied by spin coating, and dried at 55 ° C for 1 minute. The obtained unpolymerized film was confirmed to be a single region by a polarizing microscope. Then, ultraviolet rays were irradiated to produce an optical film having a film thickness of 0.9 μm. The obtained film had no elasticity and was uniformly applied, and even if it was left indoors for 30 days, peeling was not observed, the adhesion was good, and no change in optical characteristics was observed.

With respect to the obtained optical film, the incident angle dependency was measured by the above method. The inclination angle of the refractive index ellipsoid of the obtained optical anisotropy layer is shown in Table 10. With respect to the obtained film, the front retardation value R _{0 was} also measured by the above method, and the results are shown in Table 10.

[Industry use possibility]

The film of the present invention has the highest refractive index in the oblique direction with respect to the plane of the film, and is a film which can be arbitrarily controlled. Therefore, the present invention can be used as an antireflection film such as an antireflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, or the like, and an optical film having excellent wavelength dispersion characteristics. Further, the present invention can also be utilized in a phase difference plate of a reflective liquid crystal display or an organic electroluminescence display or a flat display device (FPD) having such a phase difference plate.

1, 1A, 1'‧‧‧ film

2‧‧‧ polarizing layer

3, 3'‧‧‧Next layer

4‧‧‧ polarizing film

5‧‧‧Next layer

6‧‧‧ LCD panel

7‧‧‧Lighting layer

11‧‧‧Optical anisotropic layer (liquid crystal layer)

11a‧‧‧ interface between alignment film 12 and liquid crystal layer 11

11b‧‧‧Interface of air and liquid crystal layer 11

12‧‧‧Alignment film for vertical alignment (layer)

13‧‧‧Support film

14‧‧‧ Rod-shaped polymerizable liquid crystal compound

22‧‧‧Refractive index ellipsoid

23‧‧‧Tilt angle

24‧‧‧Vertical ellipsoid

D‧‧‧ film thickness

Main refractive index of na, nb, nc‧‧‧3

Nx‧‧‧ short axis

Ny‧‧‧ long axis

Figure 1A is a cross-sectional view showing the general alignment of the film.

Fig. 1B is a cross-sectional view showing an example of the alignment of the film of the present invention.

Fig. 1C is a cross-sectional view showing another example of the alignment of the film of the present invention.

Fig. 2 is a view showing the birefringence of the film of the present invention.

Fig. 3A is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3B is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3C is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3D is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3E is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3F is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3G is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3H is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3I is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3J is a cross-sectional view showing the state of use of the film of the present invention.

Fig. 3K is a cross-sectional view showing the state of use of the film of the present invention.

Figure 4 is a cross-sectional view of a liquid crystal panel.

Fig. 5 is a cross-sectional view of an organic EL panel.

11. . . Optical anisotropic layer (liquid crystal layer)

12. . . Vertical alignment alignment film (layer)

14. . . Rod-shaped polymerizable liquid crystal compound

Claims (12)

A film having an optical anisotropic layer formed on an alignment film for vertical alignment, characterized in that a phase difference value is 50 to 400 nm; and the optical anisotropic layer is composed of a layer containing a polymer, and The polymer contains a structural unit derived from a rod-shaped polymerizable liquid crystal compound; the rod-shaped polymerizable liquid crystal compound has a horizontal alignment on a horizontal alignment film and a horizontal alignment at an air interface as a monomer. In the above, the rod-shaped polymerizable liquid crystal compound is obliquely aligned with respect to the alignment film for vertical alignment. The film according to claim 1, wherein the vertical alignment alignment film is an alignment film which is subjected to a rubbing treatment on the vertical alignment film. The film of claim 1, wherein the film angle with respect to the plane of the refractive index ellipsoid in the optical anisotropic layer is from 10° to 85°. A film having an optical anisotropic layer formed on an alignment film for vertical alignment, characterized in that a phase difference value is 50 to 400 nm; and the optical anisotropic layer is a layer containing a rod-like polymerizable liquid crystal compound The rod-shaped polymerizable liquid crystal compound has a characteristic that it is horizontally aligned on the horizontal alignment film and horizontally aligned at the air interface. The rod-shaped polymerizable liquid crystal compound is obliquely aligned with respect to the alignment film for vertical alignment. The optical film according to any one of claims 1 to 4, further comprising: an optical anisotropic layer composed of a liquid crystal, wherein the optical anisotropic layer has a first surface and a second surface parallel to the first surface And an alignment layer that is in contact with the first surface of the optical anisotropic layer; in at least a portion of the optical anisotropic layer, the liquid crystal is obliquely aligned with respect to the thickness direction; and is perpendicular to the plane of the optical film The first refractive index (nz) in one direction, the direction perpendicular to the first direction of the film, the second refractive index (nx) in the second direction, and the direction perpendicular to the first direction and the second direction of the film In the third refractive index (ny) in the third direction, the first refractive index (nz) is larger than the second refractive index (nx) and the third refractive index (ny). The film of any one of claims 1 to 4 which exhibits reverse wavelength dispersion. The film according to claim 6, wherein the optical anisotropic layer contains a polymer, and the polymer further comprises P2-E2-X2-B2-A2-(G2)tY- of the following formula (1). (G1)s-A1-B1-X1-E1-P1 (1) (wherein Y represents a divalent base, s and t are independently independent, representing an integer of 0 or 1, and G1 and G2 are independent The group represents -CR ¹ R ² -, and R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, and A1 and A2 are each independently represent a divalent cyclic hydrocarbon group. a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group, a sulfur extended phenyl group, and an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms may be bonded to A1 and A2. And a halogen atom, B1 and B2 are each independently selected from -CRR'-, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C (=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=S)-, -C(=S)-O -, -OC(=S)-, -OC(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N-, -N =N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH ₂ -, -NR-, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, a divalent group in a group consisting of a single bond, R And R' are each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X1 and X2 are each independently represented by the following formula (2) (wherein, A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, B3 represents the same meaning as the above B1 and B2, and n represents an integer of 1 to 4), and the E1 and E2 systems are independent. The olefin group having a carbon number of 2 to 25, and the E1 and E2 groups may further be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and P1 and P2 are hydrogen atoms or The polymerizable group, at least one of P1 and P2 is a structural unit derived from a polymerizable compound represented by a polymerizable group. A method for producing a film, which is a method for producing an optical anisotropic layer film formed on an alignment film for vertical alignment, having a phase difference of 50 to 400 nm, and comprising the following steps: (A) vertical alignment Coating step of coating a composition containing a rod-shaped polymerizable liquid crystal compound on an alignment film; (B) a heating step of heating the coating film formed in the above step (A) at 25 to 120 ° C for 10 seconds to 60 minutes; the rod-shaped polymerizable liquid crystal compound having a horizontal alignment on the horizontal alignment film, And the air interface is also characterized by horizontal alignment as a monomer. The method for producing a film according to the eighth aspect of the invention, which further comprises (C) a step of crosslinking the rod-shaped polymerizable liquid crystal compound by photopolymerization. The method for producing a film according to claim 8 or 9, wherein the step (A) further comprises (D) a step of subjecting the alignment film for vertical alignment to a rubbing treatment. A polarizing film obtained by laminating a film according to any one of claims 1 to 7. A flat display device comprising: a film according to any one of claims 1 to 7 or a polarizing film according to claim 11 of the patent application.