WO2007122889A1

WO2007122889A1 - Film, process for producing the film, and use of the film

Info

Publication number: WO2007122889A1
Application number: PCT/JP2007/054660
Authority: WO
Inventors: Koshiro Ochiai; Motohiro Yamahara
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2006-03-29
Filing date: 2007-03-09
Publication date: 2007-11-01
Also published as: TWI507743B; CN101410737B; TW200741264A; KR101360715B1; CN101410737A; KR20080114767A

Abstract

This invention provides a film, which can provide a high refractive index to a direction normal to the film rather than the planar direction of the film, a process for producing the film, and use of the film. A layer of a rod-like polymerizable liquid crystal compound having a hybrid alignment is formed on an aligning film for perpendicular alignment. In this case, the rod-like polymerizable liquid crystal compound is perpendicularly aligned or obliquely aligned on the interface of the aligning film for perpendicular alignment. According to the above constitution, a film can be produced which can satisfy a requirement represented by nz > nx and nz > ny wherein the refractive indexes in the orthogonal axis direction and film thickness direction of the film plane are nx, ny and nz, respectively.

Description

Specification

Film, film manufacturing method, and use thereof

Technical field

[0001] The present invention relates to a film, a film manufacturing method, and use thereof, and can provide a high refractive index in the normal direction of the film, not in the plane direction of the film, and a film manufacturing method, And its use. Background art

[0002] Flat panel display devices (hereinafter referred to as "FPD") such as liquid crystal display devices (hereinafter also referred to as "LCD") and organic electroluminescence (hereinafter referred to as "EL") are CRTs. Compared to the above, it saves space and consumes less power. Therefore, in recent years, FPD has become widespread as a screen for computers, televisions, mobile phones, car navigation systems, or personal digital assistants.

[0003] In general, various optical films are used for FPD in order to prevent reflection and widen the viewing angle. For example, anti-reflective films such as anti-reflection (hereinafter also referred to as “AR”! /, U) films that reduce the reflectivity of the surface due to the effect of light interference by multilayering optical thin film layers with different refractive indexes, specific vibration directions Polarizing film that transmits only the light of light and blocks other light, retardation film that optically compensates for interference colors of LCDs such as STN and TN systems, and polarizing film and retardation film Examples include elliptically polarizing films, and viewing angle widening films that increase the viewing angle of LCDs.

[0004] Further, the characteristics required for optical films used in FPDs differ depending not only on the functions as described above but also on the type of FPD to be applied. For example, an optical compensation film provided for developing a wide viewing angle in an LCD will be described as follows. Various LCD driving methods such as VA mode, TN mode, and IPS mode have been proposed for LCD. Each of these drive LCDs requires different characteristics for the optical compensation film provided to produce a wide viewing angle.

[0005] Specifically, in a VA mode LCD, optical compensation can be performed with a stretched film in which the refractive index is changed in the plane direction. As the above stretched film, conventionally optical compensation effect It can be used as a phase difference film that gives The stretched film can be obtained, for example, by extending a film of polybulal alcohol or polycarbonate.

[0006] In order to develop a wide viewing angle in a TN mode LCD, it is preferable to use an optical film in which the refractive index is changed in an oblique direction. Examples of such films include WV film (trade name) from Fuji Photo Film Co., Ltd. and NH film (trade name) from Nippon Oil Corporation. These films are optical compensation films that utilize the tilted orientation of liquid crystal molecules rather than stretched films. As the liquid crystal molecules, tilted aligned liquid crystal molecules that are horizontally aligned at the alignment film interface and vertically aligned at the air interface are used. Thereby, the obtained film becomes a film in which the refractive index is changed in an oblique direction.

[0007] On the other hand, in order to develop a wide viewing angle in an IPS mode LCD, an optical compensation film in which the refractive index change is small in the plane direction of the film and the refractive index is changed in the normal direction is required. . In other words, there is a need for a film that can control the tilt angle of the optically anisotropic layer, the so-called refractive index ellipsoid, in the normal direction.

[0008] However, the stretched film described above can increase the refractive index in the plane direction of the film, but cannot increase the refractive index in the normal direction of the film. For example, in the case of a polycarbonate film or the like, the refractive index cannot be increased in the normal direction of the force film that can increase the refractive index in the stretching direction. Therefore, with such a stretched film, it is not possible to achieve the wide viewing angle of the TN mode and the IPS mode LCD in the VA mode LCD.

[0009] In the case of the above-described optical compensation film using liquid crystal molecules, a rubbing treatment is performed to align the liquid crystal molecules. Therefore, the liquid crystal molecules are aligned horizontally at the alignment film interface. Therefore, when using liquid crystal molecules that are horizontally aligned at the alignment film interface and horizontally or vertically aligned at the air interface, the obtained optical compensation film is horizontally aligned and inclined. Therefore, as described above, the power that can be used to widen the TN mode LCD cannot be used for the IPS mode LCD.

[0010] As described above, the optical compensation film used in the VA mode or TN mode LCD is IPS. It cannot be used to realize a wide viewing angle for LCDs in mode. Therefore, an optical compensation film that can handle the wide field of view of IPS mode LCDs has been proposed.

Specifically, Patent Document 1 discloses that the liquid crystal compound is formed by forming a vertical alignment film using a long-chain alkyl-type dendrimer derivative and applying a polymerizable liquid crystal compound on the vertical alignment film. There is disclosed a homeo-mouth-pick-aligned liquid crystal film obtained by aligning a homeo-mouth-pick. The polymerizable liquid crystal compound is a liquid crystalline compound having, for example, an acrylate group or a metatalylate group as a polymerizable functional group, and the liquid crystalline compound is a nematic liquid crystalline compound at room temperature. It is described that things are used for prizes. Furthermore, it is described that the nematic liquid crystal material used here is coated on an alignment film together with a photopolymerization initiator to form a homeotropic alignment liquid crystal layer.

[0012] In Patent Document 2, a side chain type liquid crystal polymer is applied to a substrate on which a vertical alignment film is not provided, and the liquid crystal polymer is subjected to home-to-mouth pick alignment in a liquid crystal state, and then the alignment is performed. A home-orientated pick-aligned liquid crystal film that is fixed in a state in which the state is maintained is disclosed. Further, the side chain type liquid crystal polymer contains a monomer unit having a liquid crystalline fragment containing a monomer unit ( _a ) containing a liquid crystalline fragment side chain and a monomer unit (b) containing a non-liquid crystalline fragment side chain. It is described to do.

[0013] Patent Document 3 discloses an optical element having a light-transmitting substrate and a first birefringence layer formed on the substrate. Further, it is disclosed that the first birefringence layer has a bridged polymer force obtained by homeotropically aligning a rod-like polymerizable liquid crystal containing a coupling agent. Further, in the optical element, it is described that the cross-linked polymer has a structure in which a polymerizable liquid crystal having a rod-like molecular shape is three-dimensionally cross-linked while maintaining a homeotropic orientation. .

[0014] Further, Patent Document 4 includes a light-transmitting base material, a vertical alignment film formed on the base material, and a first birefringence layer formed on the vertical alignment film. An optical element is disclosed. Further, it is disclosed that the vertical alignment film is formed of a surfactant having a long chain alkyl group. Furthermore, it is described that the first birefringent layer has a structure in which a polymerizable liquid crystal having a rod-like molecular shape is three-dimensionally cross-linked while maintaining a homeopic orientation. Patent Document 1: Japanese Patent Laid-Open No. 2002-174724 (published on June 21, 2002) Patent Document 2: Japanese Patent Laid-Open No. 2002-174725 (published on June 21, 2002) Patent Document 3: JP 2005-165240 (published on June 23, 2005) Patent Document 4: JP 2005-165239 (published on June 23, 2005) Disclosure of the Invention

Problems to be solved by the invention

[0015] However, the vertical alignment film of the homeotopic pick alignment liquid crystal film of Patent Document 1 is formed of a long-chain alkyl dendrimer derivative. This long-chain alkyl dendrimer derivative is a special material and has a problem that it is difficult to produce. Further, the liquid crystal used in Patent Document 1 is home-to-mouth pick-aligned on the vertical alignment film, so that the alignment angle of the liquid crystal molecules cannot be adjusted. Therefore, the tilt angle of the refractive index ellipsoid with respect to the film plane in the optically anisotropic layer cannot be controlled, and the viewing angle cannot be improved in accordance with the characteristics of the liquid crystal panel.

[0016] In addition, a liquid crystal polymer is used in the manufacture of the homeotopically picked liquid crystal film of Patent Document 2. In the case of a liquid crystal polymer, in order to obtain a monodomain homeopic liquid crystal alignment, the liquid crystal polymer needs to be in a liquid crystal state, and heating at a high temperature is necessary in the liquid crystal alignment step. Therefore, it is necessary to select a substrate that can withstand the heat treatment, and a film with low heat resistance cannot be used. Moreover, since the fluidity of the liquid crystal compound is increased by raising the temperature, the adhesion to the base is lowered, or the birefringence characteristics are significantly lowered by the residual stress.

[0017] The birefringent layer of the optical element of Patent Document 3 forms a homeotopic pick alignment even if it is not on the vertical alignment film. Therefore, in order to obtain homeo-mouth pick alignment, it is necessary to mix a coupling agent in addition to the rod-like polymerizable liquid crystal. However, the birefringence anisotropy of the coupling agent is smaller than that of the rod-like polymerizable liquid crystal. Therefore, there is a problem that the retardation value of the obtained optical element is lowered. Therefore, in order to obtain a desired retardation value in the optical element, it is necessary to make the film thickness thicker than when only a rod-like polymerizable liquid crystal is used. In such an optical element, there arises a problem that light weight cannot be sufficiently achieved. In addition, the wettability to the substrate changes due to the effect of the coupling agent. The problem that a crack arises and the adhesiveness with a base | substrate will fall generate | occur | produces easily.

[0018] Furthermore, in the optical element of Patent Document 4, the vertical alignment film is formed of a surfactant. The surfactant only covers the surface of the substrate. Therefore, there is a problem that the vertical alignment film is very fragile, for example, cannot withstand a process such as rubbing. Further, since the vertical alignment film is formed of a surfactant, there is a problem that the adhesion with the birefringent layer made of a rod-like polymerizable liquid crystal compound is lacking.

As described above, the conventional optical compensation film applicable to the wide field of view of the IPS mode has various problems, and the development of a more suitable optical compensation film is demanded.

[0020] In particular, in recent years, the size of FPDs has been increasing, and new problems due to optical films have occurred. Specifically, when the size of the FPD is increased, when the entire display screen is observed from a wide angle, the display image may be colored (also referred to as a coloring phenomenon) or black and white may be reversed (also referred to as an inversion phenomenon). Problems arise. Further, when the viewing angle is tilted in the opposite viewing angle direction, which is the upper direction of the display screen, there arises a problem that the contrast is lowered. Therefore, in order to solve such problems, it is required to provide an optical film that gives optical anisotropy in an arbitrary direction without much trial and error. Furthermore, in addition to the optical compensation effect and the antireflection function, such an optical film is also required to improve the viewing angle dependency and further improve the coloring phenomenon.

[0021] The present invention has been made in view of the above problems, and is capable of giving a high refractive index in the normal direction of the film, not in the horizontal direction of the film of the optical film. It is to provide a method and use thereof.

Means for solving the problem

[0022] As a result of intensive studies in view of the above problems, the present inventors have bent in the normal direction by forming a layer of a hybrid alignment rod-like polymerizable liquid crystal compound on the alignment film for vertical alignment. The inventors have found that a film with a variable rate can be obtained, and have completed the present invention. That is, the present invention includes the following industrially useful inventions.

[0023] (1) A film having an optically anisotropic layer formed on an alignment film for vertical alignment, wherein the optically anisotropic layer comprises a polymer containing a structural unit derived from a rod-like polymerizable liquid crystal compound. The rod-like polymerizable liquid crystal compound comprising a layer containing a horizontal alignment film as a monomer When the refractive index in the orthogonal axis direction of the film plane and the film thickness direction is nx, ny, and nz, respectively, A film characterized by satisfying nz> nx and nz> ny.

[0024] (2) The finalem according to (1), wherein the alignment film for vertical alignment is a vertical alignment film.

[0025] (3) The film according to (2), wherein an inclination angle of the refractive index ellipsoid in the optically anisotropic layer with respect to the film plane is 90 ± 5 °.

[0026] (4) The film according to (1), wherein the alignment film for vertical alignment is an alignment film obtained by rubbing the vertical alignment film.

[0027] (5) The film according to (4), wherein an inclination angle of the refractive index ellipsoid in the optically anisotropic layer with respect to the film plane is 45 ° to 85 °.

[0028] (6) A film having an optically anisotropic layer formed on an alignment film for vertical alignment, the optically anisotropic layer comprising a layer containing a rod-like polymerizable liquid crystal compound, The polymerizable liquid crystal compound has the property of being aligned horizontally on the horizontal alignment film and vertically aligned at the air interface, and has a refractive index in the direction perpendicular to the film plane and in the film thickness direction. If nx, ny, nz, respectively! A film characterized by satisfying ^> 1 ^ ぉ 112> 1 ^.

[0029] (7) The film according to any one of (1) to (6), which exhibits reverse wavelength dispersion.

(8) The optically anisotropic layer has the following formula (1)

[0031] [Chemical 1]

P 2— E 2— X 2— B 2— A 2— (G 2) t— Y— (G 1) s ~ A 1 -B 1 ~ X 1— E 1— P 1 (1)

[0032] (wherein Y represents a divalent group, s and t each independently represent an integer of 0 or 1, G 1 and G2 each independently represent —CR ¹ ! ^ —, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a hydrogen atom, and A ¹ and A ² each independently represent a divalent cyclic hydrocarbon group, a divalent Represents a heterocyclic group, a methylenephenylene group, an oxy-phenylene group, a thio-phenylene group, and A1 and A2 each represent an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. Can be combined B1 and B 2 is independently CRR C≡C CH = CH— CH 2— CH 2 osc (= o) c (= o) — oo— c (= o) o— c (= o) — oc (= s ) c (= s) — oo— c (= s) o— c (= s) — o CH = N— N = CH— N = N— N (→ 0) = N— N = N (→ 0) — C (= 0) — NR NR— C (= 0) -OCH 2 NR CH 2 O

SCH 2 -CH 2 S— CH = CH— C (= 0) — O— O— C (= 0) — CH = CH Single bond force Group force selected Divalent group selected, R and R ′ are Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and XI and X2 each independently represent the following formula (2)

[0033] [Chemical 2]

[In the formula, A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, B3 represents the same meaning as B1 and B2, and n represents an integer of 1 to 4.]

E1 and E2 each independently represents an alkylene group having 2 to 25 carbon atoms, E1 and E2 are further an alkyl group having 1 to 5 carbon atoms, 1 carbon atom P1 and P2, which may be bonded to an alkoxy group of ˜5 or a halogen atom, represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group. )

(7) The film according to (7), comprising a polymer containing a structural unit derived from a polymerizable compound represented by the formula:

[0035] (9) A method for producing a film having an optically anisotropic layer formed on an alignment film for vertical alignment, comprising (A) a rod-like polymerizable liquid crystal compound on the alignment film for vertical alignment A step of applying the composition, and (B) a step of heating the coating film formed in the step (A) at 25 ° C. to 120 ° C. for 10 seconds to 60 minutes. A method for producing a film, wherein the polymerizable liquid crystal compound has a property of being oriented horizontally on a horizontally oriented film as a monomer and vertically oriented at an air interface.

[0036] (10) (C) The method further comprises a step of crosslinking the rod-like liquid crystal compound by photopolymerization. The method for producing a film according to (9).

(11) A polarization vinylom, wherein the film according to any one of (1) to (8) is laminated.

[0037] (12) A flat panel display comprising the film according to any one of (1) to (8) or the polarizing film according to (11).

(13) An optically anisotropic layer made of liquid crystal, the optically anisotropic layer having a first surface and a second surface parallel to the first surface, and the first surface of the optically anisotropic layer, A liquid crystal positioned near the first surface of the optically anisotropic layer, and aligned in the horizontal direction so as to be near the second surface of the optically anisotropic layer. The liquid crystal located is oriented almost vertically, the first refractive index (nz) in the first direction perpendicular to the optical film, the second refractive index (nx) in the second direction perpendicular to the first direction of the optical film, And, in the third refractive index (nx) in the third direction perpendicular to the first direction and the second direction of the optical film, the first refractive index (nz) is the second refractive index (nx) and the third refractive index ( nz) Larger optical film.

In one aspect of the present invention, the orientation of a liquid crystal layer after curing is controlled by controlling the orientation of a monomer or oligomer (specifically, a rod-like polymerizable liquid crystal compound) for forming a liquid crystal before curing. To control. It is considered that the orientation of the monomer before curing is the same as the orientation of the polymer after curing, that is, the liquid crystal.

The invention's effect

[0038] In the film according to the present invention, an optically anisotropic layer is formed on the alignment film for vertical alignment. The optically anisotropic layer is a layer containing a rod-like polymerizable liquid crystal compound that is horizontally aligned on the horizontal alignment film and vertically aligned at the air interface. Therefore, there is an effect that the refractive index change can be reduced in the plane direction of the film and the refractive index change can be increased in the normal direction of the film.

Brief Description of Drawings

FIG. 1A is a cross-sectional view showing an example of film orientation.

FIG. 1B is a cross-sectional view showing another example of film orientation.

FIG. 1C is a cross-sectional view showing another example of film orientation.

FIG. 2 is a diagram showing the birefringence of the film according to the present invention. FIG. 3A is a cross-sectional view showing a usage state of the film according to the present invention.

FIG. 3B is a cross-sectional view showing a usage state of the film according to the present invention.

FIG. 3C is a cross-sectional view showing a usage state of the film according to the present invention.

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

FIG. 3E is a cross-sectional view showing a usage state of the film according to the present invention.

FIG. 3F is a cross-sectional view showing a usage state of the film according to the present invention.

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

FIG. 3H is a cross-sectional view showing a usage state of the film according to the present invention.

FIG. 31 is a cross-sectional view showing a usage state of the film according to the invention.

FIG. 3J is a cross-sectional view showing a usage state of the film according to the present invention.

FIG. 3K is a cross-sectional view showing a usage state of the film according to the present invention.

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

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

FIG. 6 is a graph showing the incident angle dependence of the retardation value of the optical film produced in Example 1.

FIG. 7 is a graph showing the incident angle dependence of the retardation value of the optical film produced in Example 2.

BEST MODE FOR CARRYING OUT THE INVENTION

[0040] The embodiment of the present invention will be described as follows. The present invention is not limited to this.

<1. Film according to the present invention>

The film according to the present invention includes an optically anisotropic layer 1 formed on an alignment film for vertical alignment 1

A film having 1. The alignment film 12 for vertical alignment is formed on a support substrate. In other words, the film according to the present invention is a film in which the alignment film 12 for vertical alignment and the optically anisotropic layer 11 are sequentially laminated on the support substrate. In the film according to the present invention, the surface facing the optically anisotropic layer 11 is an air layer.

In the present specification, the “alignment film for vertical alignment” refers to an alignment film that aligns liquid crystal molecules vertically (hereinafter also referred to as “vertical alignment film”), a vertical alignment film that has been rubbed, Include It means that.

[0043] The optically anisotropic layer 11 has a layer strength containing a polymer obtained by polymerizing the rod-like polymerizable liquid crystal compound 14. As the rod-like polymerizable liquid crystal compound 14, as shown in FIG. 1A, a rod-like polymerizable liquid crystal compound having a property of being oriented horizontally on a horizontal alignment film and vertically oriented at an air interface (in the figure, an ellipse) Is used. When such a rod-like polymerizable liquid crystal compound is used, when it is aligned on a vertical alignment film (vertical alignment film) that has not been rubbed, as shown in FIG. Align vertically. In addition, when the rod-like polymerizable liquid crystal compound is aligned on a rubbing-treated vertical alignment film (alignment film for vertical alignment), as shown in FIG. While maintaining the molecular orientation in the vertical direction, it is tilted at the interface of the vertical alignment film. For convenience, in FIGS. 1A to 1C, the alignment film for vertical alignment is described as “alignment layer”, the rod-like polymerizable liquid crystal compound is described as “liquid crystal molecule”, and the optically anisotropic layer is described as “liquid crystal layer”.

[0044] Such a film according to the present invention has, as its characteristics, nz> nx and nz when the refractive indexes in the orthogonal axis direction and the film thickness direction of the film plane are nx, ny, and nz, respectively. It is a film satisfying> ny. In other words, it is a film in which the refractive index change is small in the plane direction of the film and the refractive index change is large in the normal direction of the film. Therefore, the film according to the present invention has an effect that the refractive index change is large in the normal direction of the film and the refractive index change is small in the plane direction of the film. Therefore, the film according to the present invention can be used as an optical film suitable for a liquid crystal panel such as an IPS mode.

[0045] In addition, the film according to the present invention has optical anisotropy! /. Examples of the optical anisotropy include a tilt angle and a phase difference value. The optical anisotropy of the film that is useful in the present invention will be described in more detail with reference to FIG.

As shown in FIG. 2, in the refractive index ellipsoid 22 showing the optical characteristics of the film 1, three-dimensional main refractive indexes na, nb, and nc are defined. The angle between the Y axis and the main refractive index nb is defined as the tilt angle 23, and the vertical ellipsoid formed on the film when viewed from the Z direction is defined as the major axis ny and minor axis nx of the ny. And the product of film thickness d (ny— nx) 'd is defined as the phase difference value.

[0047] Examples of the method for measuring the phase difference value include a method such as ellipsometer measurement. The tilt angle can be measured by, for example, measuring the dependence on the incident angle of light in the measurement of the phase difference value, and using the calculated value of the change in the phase difference value of the ideal refractive index ellipsoid depending on the incident angle. For example, a method of calculating the force.

[0048] Usually, the retardation value is about 5 to 700 nm, preferably about 50 to 400 nm.

[0049] Here, the support substrate, the alignment film for vertical alignment, and the optically anisotropic layer constituting the film according to the present invention will be described in more detail below.

[0050] (I 1) Support base material

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 translucent film can be mentioned. Examples of the translucent film include polyolefin films such as polyethylene, polypropylene, and norbornene polymers, polybutyl alcohol films, polyethylene terephthalate films, polymethacrylate films, polyacrylate films, and cellulose esters. Film, polyethylene naphthalate film, polycarbonate film, polysulfone film, polyethersulfone film, polyetherketone film, polyphenylene sulfide film, polyphenylene oxide film, and the like.

[0051] In general, an optically anisotropic layer using a polymerizable liquid crystal compound is a thin film, and includes, for example, a film forming process using a film of the present invention, a process of transporting and storing the film, and the like. Even a process that requires high strength can be handled easily without tearing by using a support substrate.

[0052] (I 2) Alignment film for vertical alignment

In the film of the present invention, the alignment film for vertical alignment must have solvent resistance that does not dissolve when coated with an optically anisotropic layer or the like, and has heat resistance due to solvent removal or liquid crystal alignment heat treatment. Further, it is necessary that the film does not peel off due to friction due to rubbing, etc., and is a polymer or a composition containing a polymer.

[0053] The polymer is not particularly limited as long as it is formed on the support substrate. For example, polyamides and gelatins with amide bonds in the molecule, Examples thereof include a polyimide having an imide bond and a hydrolyzate thereof such as polyamic acid, polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polyacrylic acid, and polyacrylic acid esters. These polymers may be used alone, or two or more of them may be mixed or copolymerized. These polymers can be easily obtained by polycondensation such as dehydration or deamination, chain polymerization such as radical polymerization, cation polymerization, and cation polymerization, coordination polymerization, and ring-opening polymerization.

[0054] Such a polymer can introduce an organic group such as an alicyclic group such as a steroid, a long-chain alkyl group, a fluorinated alkyl group, an aromatic ring structure and a fluorine-containing aromatic ring structure. . By introducing the structure as shown above, the rod-like polymerizable liquid crystal compound is more easily vertically aligned. In addition, compounds containing organic groups such as alicyclic groups such as steroids, long-chain alkyl groups, alkyl fluoride groups, aromatic ring structures and fluorine-containing aromatic ring structures may be mixed, or onium salts, cesium ions, rubidium ions. The rod-like polymerizable liquid crystal compound also becomes more vertically oriented by using a composition to which an inorganic salt or organic acid salt such as the above is added.

[0055] Specific examples of the polymer include polyimides disclosed in, for example, JP-A-2001-305549, WO20 03-042752, JP-A-2005-139228, Liquid Crystal No. 8-4, page 216, and the like. Examples thereof include polyamic acid, and polybutyl alcohol disclosed in JP-A-2005-196015, JP-A-2005-315988, JP-A-2005-196016, and the like. Further, a polyimide alignment film for vertical alignment (trade name SE-5300, manufactured by Nissan Chemical Co., Ltd.) used in Examples described later is also a polyimide alignment film for vertical alignment.

[0056] The thickness of the alignment film for vertical alignment is not particularly limited, but ΙΟηπ! ˜lOOOOnm is preferred. 10 nm to 1000 nm is more preferred. If it is within the above range, the obtained film can be reduced in weight. Further, the influence of the optical characteristics of the alignment film for vertical alignment on the resulting film can be reduced.

[0057] The alignment film for vertical alignment may be rubbed as necessary. When a rod-like polymerizable liquid crystal compound, which will be described later, is aligned in a liquid crystal state on an alignment film for vertical alignment that has not been subjected to a rubbing treatment, the rod-like polymerizable liquid crystal compound is converted into a vertical alignment film. On the other hand, it is nematically aligned vertically. Therefore, the film obtained is a vertically oriented film.

On the other hand, when a rod-like polymerizable liquid crystal compound, which will be described later, is oriented in a liquid crystal state on a rubbing-treated vertical alignment film, the rod-like polymerizable liquid crystal compound is oriented vertically at the air layer interface. In this state, tilt alignment is performed at the alignment film interface for vertical alignment. Therefore, the obtained film becomes a tilted orientation film.

[0059] That is, the film of the present invention includes both a vertically oriented film and a tilted oriented film.

[0060] (I 3) Optically anisotropic layer

The optically anisotropic layer is a layer having optical anisotropy formed on the alignment film for vertical alignment. The optically anisotropic layer is a layer containing a polymer containing a structural unit derived from a rod-like polymerizable liquid crystal compound. The optically anisotropic layer may contain a polymer containing a structural unit derived from a compound other than the rod-like polymerizable liquid crystal compound. For example, in order to impart desired wavelength dispersion characteristics to the film of the present invention, a polymer containing a structural unit derived from a specific polymerizable compound may be used as the structural unit derived from a rod-like polymerizable liquid crystal compound. Good. In addition, a liquid crystal compound different from the rod-like polymerizable liquid crystal compound and the specific polymerizable compound (hereinafter also referred to as “other liquid crystal compound” for convenience of explanation) may be included. Furthermore, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent and the like may be contained. The details of the compound constituting the optically anisotropic layer will be described later.

[0061] The thickness of the optically anisotropic layer may be adjusted as appropriate so that the retardation value (retardation value, Re (λ)) of the obtained film becomes a desired value. Re (λ) is determined by the following equation (a). In other words, the film thickness d may be adjusted in order to obtain the desired Re ().

[0062] Re () = d X Δ η (λ) · · · (&)

(In the formula, Re (λ) represents a retardation value at a wavelength of λ nm, d represents a film thickness, and Δη (λ) represents a refractive index anisotropy at a wavelength of ληπι.)

In a preferred embodiment of the film according to the present invention, the alignment film for vertical alignment is a vertical alignment film, and the refractive index ellipsoid of the rod-like polymerizable liquid crystal compound is a film. It is preferable to have an inclination angle of 90 ± 5 ° with respect to the plane. As a result, the film

It becomes a vertically oriented film.

[0063] In another embodiment, the alignment film for vertical alignment is a rubbing-processed vertical alignment film, and the refractive index ellipsoid of the rod-like polymerizable liquid crystal compound is not aligned on the alignment film interface for vertical alignment. The film preferably has an inclination angle of 45 ° to 85 ° with respect to the plane of the film. As a result, the film becomes a tilted orientation film.

Hereinafter, the rod-like polymerizable liquid crystal compound, other liquid crystal compound, polymerizable compound, and other constituent compounds that can be contained in the optically anisotropic layer will be described in detail.

[0065] (1-3-1) Rod-like polymerizable liquid crystal compound

The rod-like polymerizable liquid crystal compound contained in the optically anisotropic layer is a rod-like polymerizable liquid crystal compound that is oriented horizontally on the horizontally oriented film as a monomer and vertically oriented at the air interface. The above “rod-like polymerizable liquid crystal compound that is aligned horizontally on a horizontal alignment film as a monomer and vertically aligned at an air interface” means, for example, polyvinyl chloride as a horizontal alignment film on a glass substrate whose surface is horizontally processed or on the surface. The orientation obtained when a rod-like polymerizable liquid crystal compound is applied as a monomer on a substrate provided with an orientation film that induces horizontal orientation such as alcohol is horizontal on the orientation film, and the rod-like polymerizability is oriented vertically at the air interface. It is a liquid crystal compound. The rod-like polymerizable liquid crystal compound maintains a strong orientation even when polymerized, and gives a high refractive index in the normal direction of the film.

[0066] Such a so-called polymerizable liquid crystal compound imparting noble orientation is a single or a liquid crystal containing a structural unit derived from two or more kinds of rod-like polymerizable liquid crystal compounds. — 320317 discloses polymerizable liquid crystal compounds disclosed in JP-A-2001-55573. Further, the orientation may be controlled by adding a silicon-based oligomer compound, a fluorine-containing polymer, a (meth) acrylic monomer, a nonionic surfactant, or the like to the rod-like polymerizable liquid crystal compound. Examples of such a method include methods disclosed in Japanese Patent Application Laid-Open Nos. 9-288210, 2006-16599, and 2005-196221.

[0067] Specific examples of the rod-like polymerizable liquid crystal compound include a liquid crystal manual (Liquid Crystal Handbook Editorial Committee). Chapter 3, published by Maruzen Co., Ltd. (October 30, 2000)) Chapter 3 Molecular structure and liquid crystallinity, 3.2 Non-chiral rod-like liquid crystal molecules, 3.3 Polymerization among the compounds described in Chiral rod-like liquid crystal molecules And compounds having a group.

More specifically, a rod-like polymerizable liquid crystal compound contained in RMS-03-011 (trade name, manufactured by Merck & Co., Inc.) used in Examples described later can be given.

[0069] In the film according to the present invention, as the rod-like polymerizable liquid crystal compound, the above-described rod-like polymerizable liquid crystal having a high-order alignment, which is not a conventional rod-like polymerizable liquid crystal compound having a home-to-mouth orientation, is used. By using the compound, the inclination angle of the refractive index ellipsoid in the optically anisotropic layer obtained by polymerizing the compound can be arbitrarily controlled in the normal direction. More specifically, when the rod-shaped polymerizable liquid crystal compound is aligned in a liquid crystal state on the vertical alignment film that has not been rubbed among the alignment films for vertical alignment, the rod-shaped polymerizable liquid crystal compound is vertically aligned. After nematic vertical alignment with the alignment film for use, the film is polymerized while maintaining the alignment. On the other hand, when the rod-like polymerizable liquid crystal compound is aligned in a liquid crystal state on the rubbing-treated vertical alignment film, the rod-like polymerizable liquid crystal compound remains vertically aligned at the air layer interface. At the alignment film interface for alignment, the film is tilted and then polymerized while maintaining the orientation to give a finalem.

Therefore, the film according to the present invention has a small change in refractive index in the plane direction of the film, and a film having a large change in refractive index in the normal direction of the film.

[0071] The rod-like polymerizable liquid crystal compound may be polymerized by any polymerization mode. For example, a thermally polymerizable rod-like polymerizable liquid crystal compound and a photopolymerizable rod-like polymerizable liquid crystal compound can be exemplified. In the present invention, a photopolymerizable rod-like polymerizable liquid crystal compound is particularly preferable. According to this, the rod-like polymerizable liquid crystal compound can be polymerized at a low temperature and fixed. Therefore, the range of selection of the support substrate is widened, and at the same time, it is industrially advantageous.

[0072] (I 3-2) Other liquid crystal compounds

The polymer containing the structural unit derived from the rod-like polymerizable liquid crystal compound contained in the optically anisotropic layer contains structural units derived from different types of liquid crystal compounds. May be.

[0073] The liquid crystal compound includes, for example, the following formula (3), formula (4), formula (5), formula (6), formula (7), or formula (

8) is preferred.

[0074] Pll- Ell- Bll- All- B12- A12- B14- A14- B15- E12- P12 (3)

PI 1- El 1-Bll-Al 1- B12- A12- B14- A14- B13- Fl 1 (4)

PI 1-Bll-Al 1-B12-A12-B14-A14-B13-F11 (5)

Pll- Ell- Bll- All- B12- A12- Fll (6)

PI 1-Bl 1-Al 1-B12-A12-B13-F11 (7)

PI 1- El 1-Bll-Al 1- B12- A12- B13- Fl 1 (8)

In the above formula (3), formula (4), formula (5), formula (6), formula (7) and formula (8), Al l A 12 and A14 are each independently a bivalent It represents a cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group, or a thiophenylene group. Al l A12 and A14 may be bonded to a C 15 alkyl group, a C 15 alkoxy group, or a halogen atom.

[0075] Bl l B12 B13 B14 and B15 are independently CRR C≡C

CH = CH CH— CH O S C (= 0) C (= 0) — O

twenty two

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 (→ 0) = N N = N (→ 0) C (= 0) — NR NR— C (= 0) OCH NR CH O SCH CH S CH = CH— C (=

2 2 2 2

0) —0—0—C (= 0) —CH = CH—, and a group consisting of a single bond (where R and R ′ each independently represents a hydrogen atom or an alkyl group having 14 carbon atoms) Represents a selected divalent group.

[0076] E11 and E12 each independently represents an alkylene group having 225 carbon atoms. More

E11 and E12 may be bonded with a C 15 alkyl group, a C 15 alkoxy group, or a halogen atom! /.

[0077] P 11 in the formula (4) (8) represents a polymerizable group. In formula (3), P11 and P12 represent a hydrogen atom or a polymerizable group, and at least one of P11 and P12 is a polymerizable group. [0078] Fl 1 represents a hydrogen atom, a halogen atom such as an alkyl group, a nitrile group, a nitro group, a trifluoromethyl group, a fluorine atom or a hydrogen atom.

[0079] Other liquid crystal compounds include, among others, the following formulas (3-1) to (3-6), formulas (6-1), formulas (6-2), formulas (8-1), and formulas (8-2)

[0080] [Chemical 3-1]

2 (3- D 3- 2)

C3- 4)

_{H 2 C = CH -COO - (} CH 2) i-0C00 ^ COO OCOO - (CH 2) i-OCO - CH = CH; C3- 5)

[0081] A liquid crystal compound represented by any one of the following formulas (3-7) to (3-12), (4 1) to (4 4

), Formula (5-1), formula (5-2), formula (7-1), and formula (7-2)

[0082] [Chemicalization 4-1]

卜

I CO CO

_

H "

Ye

(S I c 5 "

(Hεon-r

[Chemical 4-2]

H ^ = CH ^: OOi: CH ^ ~ O HCOO-> ~ OCO-i ^ -OC ^ H _1T (4 1 1)

[0084] (I 3-3) Polymerizable compound

As the polymer of the optically anisotropic layer, a polymer further containing a structural unit derived from a specific polymerizable liquid crystal compound may be used in order to impart desired wavelength dispersion characteristics of the obtained film.

The “specific polymerizable compound” is a compound that can be used in combination with the rod-like polymerizable liquid crystal compound to impart desired wavelength dispersion characteristics to the resulting film.

[0086] Examples of such polymerizable compounds include the following formula (1):

[0087] [Chemical 5]

P 2-E 2— 2-B2-A2- (G2) t— Y— (G l) s -.- A 1— B 1—: X 1— E 1— P 1 (1)

[0088] (wherein Y represents a divalent group, s and t each independently represent an integer of 0 or 1, G 1 and G2 each independently represent —CI ^ R ² — ( R ¹ and R ² each independently represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a hydrogen atom), and A1 and A2 each independently represent a divalent cyclic hydrocarbon group, Represents a divalent heterocyclic group, methylene phenylene group, oxy-phenylene group, or thio-phenylene group, and A1 and A2 include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or B1 and B2, which may be bonded to halogen atoms, are independently -CRR 'C≡CCH = CH—, -CH -CH OSC (= 0) C (= 0) — O

twenty two

o c (= o) o c (= o) — o c (= s) c (= s) o o—

C (= S) O— C (= S) — O CH = NN = CH N = NN (→ 0) = NN = N (→ 0) C (= 0) — NR NR— C (= 0) OC H NR—, -CH O—, -SCH CH S CH = CH— C (= 0) — O

2 2 2 2

0—C (= 0) —CH = CH—, and a group consisting of a single bond (where R and R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). XI and X2 are each independently represented by the following formula (2)

[0089] [Chemical 6]

[0090] (wherein A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, and B3 represents CRR 'C≡C CH = CH—, -CH -CH OSC (= 0) C

twenty two

(= o) — ooc (= o) oc (= o) — oc (= s) c (= s) OO— C (= S) O— C (= S) — O CH = NN = CH N = NN (→ 0) = NN = N (→ 0) C (= 0) — NR NR— C (= 0) -OCH NR -CH O—, -SCH CH S CH = C

2 2 2 2

H—C (= 0) —O—, —O—C (= 0) —CH = CH—, and a group consisting of a single bond (where R and R ′ are each independently a hydrogen atom or a carbon number of 1 to 4 represents an alkyl group of 4) represents a divalent group selected from n, and n represents an integer of 1 to 4)

E1 and E2 each independently represents an alkylene group having 2 to 25 carbon atoms, and E1 and E2 each represents an alkyl group having 1 to 5 carbon atoms, carbon P1 and P2, which may have an alkoxy group of 1 to 5 or a halogen atom bonded thereto, represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group. ).

[0091] Y in the above formula (1) represents a divalent group, and this group preferably has a bent structure. Here, the “bending structure” is an angle formed from a linking group that is a bonding group of Y and bonded to a group containing A1, and a linking group that is a bonding group of Y and bonded to a group containing A2. It means a structure with a force of 100 ° to 140 °. The angle is preferably 110 ° to 130 °. Within the above range, the compatibility when the polymerizable compound and the rod-like polymerizable liquid crystal compound are dissolved in an organic solvent is improved. Therefore, the retardation value of the obtained film can be improved.

[0092] As specific Y, the following formula (9)

[0093] [Chemical 7]

Dl D2

\ /

z ^cl \ ⁽⁹⁾

[0094] and the like.

[0095] A linking group that binds to a group that includes Y and a bond that binds to Y, and a bond that binds to Y and includes A2. The angle formed from the bonding group bonded to the base group is expressed by Al, A2, Cl, Dl, D2, (Gl) s, (G2) t. In the above formula (1), s = t = l In some cases, the angle can be represented by a double-headed arrow in the following formula (91). Similarly, when s = t = 0 in the above formula (1), the angle can be expressed by the following formula (92).

[0096] [Chemical 8]

[0097] In the above formula (9), C1 represents a quaternary carbon atom or a quaternary key atom. Of these, C1 is preferably a quaternary carbon atom because it is easy to produce.

[0098] In the above formula (9), each of D1 and D2 represents a cyclic hydrocarbon group, a heterocyclic group, a linear hydrocarbon group having 1 to 5 carbon atoms, or a branched carbon group having 1 to 5 carbon atoms. Represents a hydrogen group. Examples of the cyclic hydrocarbon group used for D1 and D2 include a cycloalkyl group having about 5 to 12 carbon atoms such as a cyclopentyl group and a cyclohexyl group;

[0099] [Chemical 9]

[0100] An aromatic group having about 6 to 18 carbon atoms represented by any one of

[0101] The heterocyclic group used for D1 and D2 includes the following formulas such as 5-membered ring and 6-membered ring:

.

[0103] Examples include groups represented by deviations.

[0104] D1 and D2 may be linked by a hydrocarbon group having 1 to 5 carbon atoms, an amino group, an ether group, a thioether group, or a single bond. D1 and D2 include a hydroxyl group, an amino group, a thiol group, a cyclic hydrocarbon group, a linear or branched alkyl group having 1 to 5 carbon atoms, and a linear or branched structure having 1 to 5 carbon atoms. An alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom may be bonded.

Here, examples of the hydrocarbon group include an alkylene group such as a methylene group, an ethylene group, and a propylene group, and a linking group in which a single bond of an alkylene group is substituted with a double bond or a triple bond. it can. Examples of the cyclic hydrocarbon group include the same cyclic hydrocarbon groups as those used for D1 and D2. As the alkyl group, alkoxy group and halogen atom, the alkyl group, alkoxy group and halogen atom exemplified as the group substituted by A1 and A2 can be exemplified.

Specific examples of the group represented by the above formula (9) include the following formulas (D-1) to (D-18)

[0107] [Chemical 11]

(D-2) (D-3) (D-4) (D-5)

(D— 1 5) (D- 6) (D- l 7) (D- l 8)

[0108] is a divalent substituent (here, as a quaternary atom C1, a carbon atom is illustrated because it is easy to produce), C1 is a carbon atom, and D1 and D2 are Substituents, both of which are phenol groups, can be mentioned.

[0109] Note that some of the hydrogen atoms contained in the exemplified structures are alkyl groups having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, and a t-butyl group; a methoxy group and an ethoxy group. An alkoxy group having about 1 to 4 carbon atoms such as a group; a trifluoromethyl group; a trifluoromethyloxy group; a nitrile group; a nitro group; and a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. Yo ...

[0110] From the viewpoint of ease of production, Y is a substituent in which C1 is a carbon atom, and D1 and D2 are both phenyl groups, or represented by the above formulas (D-1) to (D-12). It is preferable that it is a substituent. In particular, the substituents represented by the above formulas (D-1;) to (D-12) are preferable from the viewpoint of remarkably showing reverse wavelength dispersion. [0111] In (Gl) s and (G2) t in the above formula (1), s and t each independently represents an integer of 0 or 1.

[0112] When s and t are 1, G1 and G2 are each independently —CI ^ R ² —. Here, R ¹ and R ² each independently represents an alkyl group having about 1 to 4 carbon atoms such as a methyl group or an ethyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

[0113] When s and t are 0, Y and A1 are single-bonded, and Y and A2 are single-bonded.

[0114] In the above formula (1), A1 and A2 each independently represent a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylene-phenylene group, an oxy-phenylene group, or a thio-phenylene group. To express. Here, the methylene group, the ether group, and the thioether group in the methylenephenylene group, the oxyphenylene group, or the thiophenylene group are bonded to B1 and B2.

[0115] Examples of the divalent cyclic hydrocarbon group used for A1 and A2 include the following formulas:

[0116] [Chemical 12]

[0117] An aromatic group having about 6 to 18 carbon atoms represented by any one of the following formulas:

[0118] [Chemical 13]

[0119] An alicyclic group composed of a 5-membered ring and a 6-membered ring represented by

[0120] [Chemical 14]

[0121] Powerful heterocyclic groups such as the 5-membered ring and 6-membered ring represented by any of the above can be mentioned.

[0122] In addition, as A1 and A2, a part of the hydrogen atoms of the above exemplified group is a carbon group such as a methyl group, an ethyl group, an i-propyl group, a t-butyl group, or an alkyl group having about 1 to 4 ; Alkoxy group having about 1 to 4 carbon atoms such as methoxy group and ethoxy group; trifluoromethyl group;

/ 厂

Nitromethyloxy group; nitrile group; nitro group; substituted with a halogen atom such as a fluorine atom, a salt T element-atom, or a bromine atom.

[0123] From the viewpoint of ease of production, both A1 and A2 are preferably the same type of group.

. In particular, A1 and A2 are preferably a 1,4-phenylene group, a 1,4-cyclohexylene group, or a divalent group substituted with ~ 3 nitrogen atoms of a benzene ring carbon atom. Gu

It is more preferable that it is a 1,4-phenylene group.

[0124] B1 and B2 are each independently CRR C≡C― CH = CH― C

H CH O S C (= 0) C (= 0) — O O— C (= 0) —

twenty two

oc (= o) — oc (= s) c (= s) ooc (= s) o C (= S) — O CH = NN = CH N = NN (→ 0) = NN = N (→ 0) C (= 0) — NR NR— C (= 0) OCH NR

2

CH O SCH CH S CH = CH— C (= 0) — O O— C (=

2 2 2

O) —CH═CH—, a divalent group selected from the group consisting of a single bond. Here, R and R ′ each independently represent 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.

[0125] From the viewpoint of ease of production, B1 and B2 are both divalent groups of the same type. And are preferred.

In the above formula (1), when s and t are 0, B1 and B2 are preferably —CRR ′ 1, —O—, 1 S or NR—.

[0127] When B1 and B2 are the above-mentioned bonding groups, the connecting portion between Al (A2) and Bl (B2) and the connecting portion between Bl (B2) and XI (X2) are bent, Since the angle generated in the linking group Y can be changed, it is preferable that the compatibility with the rod-like polymerizable liquid crystal compound to be mixed tends to be improved.

[0128] In the above formula (1), when s and t are 1, and preferably when G1 and G2 are methylene groups, B1 and B2 are a single bond, C≡C , −0-C (= 0) —O, —oc (= o), or Oc (= o) —O.

[0129] When B1 and B2 are the above linking groups, the production is easy, and X2—B2 in the above formula (1)

Since A2 and Al-Bl-XI are each linear, it is preferable that they have a tendency to improve the orientation.

[0130] XI and X2 in the above formula (1) are represented by the following formula (2)

[0131] [Chemical 15]

[0132] represents a divalent group represented by:

[0133] In the above formula (2), A3 represents a divalent cyclic hydrocarbon group or a divalent heterocyclic group. Specifically, examples of A3 include the same divalent cyclic hydrocarbon groups and divalent heterocyclic groups exemplified in A1 and A2. From the viewpoint of ease of production, it may be a 1,4-phenylene group, 1,4-cyclohexylene group, or a divalent group in which 1 to 3 carbon atoms of the benzene ring are substituted with nitrogen atoms. The preferred 1,4-phenolene group is even more preferred.

[0134] From the viewpoint of ease of production, both XI and X2 are preferably the same type of divalent group.

[0135] B3 can be defined in the same way as B1. Above all, from the viewpoint of ease of manufacture, O c (= o) —, 1 c (= o) — o—, 1 o—, or a single bond is preferable.

[0136] n represents an integer of 1 to 4. When n is 2 or more, compounds (1 2) to (1

Like in (4), the structural units consisting of A3 and B3 are different from each other! /, May! /.

[0137] When casting the composition containing the resulting polymerizable compound, n is preferably 1 or 2 from the viewpoint of easy handling. Furthermore, n is preferably 1 from the viewpoint of ease of production.

[0138] E1 and E2 each independently represent an alkylene group having 2 to 25 carbon atoms, preferably an alkylene group having 4 to 10 carbon atoms.

[0139] The hydrogen atom of E1 and E2 is substituted by an alkyl group, an alkoxy group, a trifluoromethyl group, a trifluoromethyloxy group, a nitrile group, a nitro group, or a halogen atom! Okay, but it's preferable to remain a hydrogen atom!

[0140] It is preferable that E1 and E2 are both the same type of alkylene group because production is easy.

[0141] P1 and P2 represent a hydrogen atom or a polymerizable group.

In the present specification, the “polymerizable group” means a substituent capable of polymerizing the polymerizable compound and the rod-shaped polymerizable liquid crystal compound described above. Specifically, vinyl group, p-stilbene group, attalyloyl group, methacryloyl group, carboxyl group, methyl carbo yl group, hydroxyl group, amide group, C1-C4 are also alkylamino group, amino group, epoxy group, oxetanyl. Examples include groups, aldehyde groups, isocyanate groups, and thioisocyanate groups.

[0143] In order to link the above-exemplified group and E1 or E2 to the polymerizable group, B1 or

The groups exemplified in B2 may be included.

[0144] Among them, an attaloyl group is more preferable, in which an allyloyl group or a methacryloyl group is preferable. If these groups are used, the handling during photopolymerization is easy and the production is also easy.

[0145] At least one of P1 and P2 is preferably a polymerizable group, and it is more preferable that both P1 and P2 are a polymerizable group. Thereby, the film hardness of the obtained film can be made favorable. [0146] Specific examples of the polymerizable compound include the compounds shown in Tables 1 to 4.

[0147] [Table 1-1]

PS0 / L00Zd £ / 13d 98 OAV ίζ-zm

099 ^ S0 / L00rdf / I3d ε 688 peristaltic OAV

[Table 2-3]

[ΐ— ε 挲] [6wo]

099tS0 / L00Zd £ / ∑Jd OP OAV

z-zm

099tS0 / L00Zd £ / ∑Jd IP OAV [Table 3-3]

/ v: / O 0991so / -ooifcl £ 6883ϊ / -00ίAV 377 ¾0ΐο3

Examples of polymerizable compounds (Part 4)

[0151] The optically anisotropic layer may contain any one of structural units derived from the polymerizable compound, but may be derived from a plurality of different polymerizable compounds. Structural units may be included. Among these, it is preferable that structural units derived from the compounds described in Tables 1 and 2 are included. If such a compound is used, the film which is useful in the present invention can remarkably exhibit reverse wavelength dispersion. Furthermore, it is more preferable to include structural units derived from the compounds shown in Table 1. If such a compound is used, a film that can be used in the present invention can be easily produced.

[0152] Here, the notation of the table will be described by taking the compound (1-1) as an example. “A1 = A2” means that A1 and A2 are the same phenylene group. “A side of B1 = B2” means that the ether part of the ester group is bonded to A (a phenylene group). “B1 = X side of B2” means that the carbo moiety of the ester group is bonded to X (phenylene ether group). Further, when there is no designation of the side, it indicates that the direction may be replaced in any direction.

[0153] As the polymerizable compounds, the compounds shown in Table 1 or 2 are preferred, and the compounds shown in Table 1 are more preferred. The following formulas (1 1) and (1-2) , (1-3), (1 -4), (1-5), (1 11), (1-45), (1-49), and (1-50) are particularly preferred. .

[0154] [Chemical 16— 1]

[Chemical 16—2]

[0155] Like the compound represented by the above formula (11), the method for producing a polymerizable compound in which s = t = 0 in the above formula (1) includes, for example, the structures of Cl, D1, and D2. The corresponding carbonyl compound is used as the compound that gives the compound, and the halide of the compound containing Al (A2), Bl (B2), XI (X2), El (E2) and PI (P2) acts on the carbonyl compound. And a method obtained by dehydration condensation. Compounds containing Al (A2), Bl (B2), XI (X2), El (E2) and PI (P2) are Al (= A2), B1 (= B2), XI (= X2), E1 (= E2), PI (= P2) containing a structural unit of dehydration condensation reaction, ester reaction, Williamson reaction, Ullmann reaction, benzylation reaction, fungus head reaction, Suzuki Ichinomiyaura reaction, Negishi reaction, Kumada reaction, It can be produced by combining by the Hiyama reaction, the Buchwald-Hartwig reaction, the Witstig reaction, the Friedel-Craft reaction, the Heck reaction, or the aldol reaction.

[0156] Like a compound represented by the above formula (12), a polymerizable compound in which s and t in the above formula (1) are 1, and G1 and G2 are both methylene chains As a production method, for example, a halogenobenzyl having iodine in a benzene ring as an alkali metal hydroxide is used as a compound that gives structural units of C2 and Al (C3 and A2) to the carbonyl compound. And compound containing Al (A2), Cl, Gl (G2), D1 and D2, and separately synthesized Bl (B2), XI (X2), El (E2) and PI (P2) From compounds containing Al, A2, Cl, Gl, G2, Dl, and D2 obtained in the same manner, from B 1 (B2), XI (X2), El (E2) and PI Examples thereof include a method of sequentially reacting a compound giving the structure of (P2).

[0157] The wavelength dispersion characteristic of the obtained film is determined by the proportion of the structural units derived from the rod-like polymerizable liquid crystal compound and the polymerizable compound. In the present invention, when the polymerizable compound is not contained, the resulting film is a film exhibiting positive wavelength dispersion. On the other hand, by increasing the content of the structural unit derived from the polymerizable compound, the wavelength dispersion characteristic can be arbitrarily adjusted from the normal wavelength dispersion to the reverse wavelength dispersion. Therefore, the film according to the present invention preferably contains the polymerizable compound in an amount that provides desired wavelength dispersion characteristics. The content of the polymerizable compound necessary for imparting a desired wavelength dispersion characteristic can be determined as follows. Example For example, the ratio of the structural unit derived from the polymerizable compound contained in the composition containing the rod-like polymerizable liquid crystal compound and the polymerizable compound is adjusted, and the retardation value of the resulting film is obtained. From the result, the content of the structural unit derived from the polymerizable compound can be determined.

[0158] (I 3-4) Other constituent compounds

(Polymerization initiator)

The optically anisotropic layer may contain a polymerization initiator for polymerizing the rod-like polymerizable liquid crystal compound or the polymerizable compound. The polymerization initiator is not particularly limited as long as it can be used for polymerizing the compound. Preferable film which is useful in the present invention U. As one embodiment, the rod-like polymerizable liquid crystal compound is preferably photopolymerized. Therefore, the polymerization initiator is preferably a photopolymerization initiator.

[0159] Examples of the photopolymerization initiator include benzoins, benzophenones, benzyl ketals, α-hydroxy ketones, α-amino ketones, iodine salts, sulfo-um salts, and the like. Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 250, and Irgacure 369 (all from Ciba Specialty Chemicals Inc.), Sake All BZ, Sake All Z, Sake All BEE (and all above) ), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), KYACURE I UVI—6992 (manufactured by Dow), Adekaoptomer SP—152, Adekaoptomer SP—170 (all above, Asahi Denka) And so on.

[0160] By using such a photopolymerization initiator, the rod-like polymerizable liquid crystal compound and the polymerizable compound can be photopolymerized. In addition, the content of such a polymerization initiator is 10% by weight or less with respect to the liquid crystal compound-containing composition described later, because the orientation of the rod-like polymerizable liquid crystal compound is not disturbed. Is preferred.

[0161] [Polymerization inhibitor]

The optically anisotropic layer may contain a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinones having a substituent such as hydroquinone and alkyl ether, and substituents such as alkyl ether such as butylcatechol. Catechols, pyrogallols, 2,2,6,6, -tetramethyl-1-piberidyl-roxy radicals, thiophenols, β-naphthylamines, and j8-naphthols.

[0162] By using the polymerization inhibitor, the polymerization of the rod-like polymerizable liquid crystal compound or the polymerizable compound can be controlled, and the stability of the optically anisotropic layer can be improved.

[0163] [Photosensitizer]

The optically anisotropic layer may contain a photosensitizer. The photosensitizer is not particularly limited, and examples thereof include xanthones such as xanthone and thixanthone, anthracenes having a substituent such as anthracene and alkyl ether, phenothiazine, and rubrene. .

[0164] By using the photosensitizer, the sensitivity of the polymerization of the rod-like polymerizable liquid crystal compound or the polymerizable compound can be increased.

[Leveling agent]

Further, the optically anisotropic layer may contain a leveling agent. The above-mentioned leveling agent is not particularly limited, and a conventionally known leveling agent can be added. Examples of the leveling agent include additives for radiation-curing coatings (by Big Chemie Japan: ΒΥΚ-352, BYK-353, BYK-361N), coating additives (from Toray Dowco Jung: SH28PA, DC 11 PA). , ST80PA), and paint additives (manufactured by Shin-Etsu Silicone: KP321, ΚΡ323, ΚΡ22-161A, KF6001).

[0166] By using the leveling agent, the optically anisotropic layer can be smoothed. Furthermore, in the process of producing the film, the fluidity of the liquid crystal compound-containing composition described later can be controlled, and the crosslink density of the rod-like polymerizable liquid crystal compound or polymerizable compound can be adjusted.

<11. Method for producing film that is useful in the present invention>

The method for producing a film according to the present invention can be suitably used for producing the above-described film according to the present invention. Specifically, (i) a step of applying the above-described composition containing the rod-like polymerizable liquid crystal compound on the alignment film for vertical alignment (hereinafter, “liquid crystal compound-containing composition application step” t, u), (B) Liquid crystal compound-containing composition coating And a step of heating the coating film formed at 25 ° C. to 120 ° C. for 10 seconds to 60 minutes (hereinafter, also referred to as “(liquid crystal compound-containing composition heating step)”).

[0168] According to the above configuration, when a vertical alignment film is used as the vertical alignment film, the rod-like polymerizable liquid crystal compound can be nematically aligned vertically on the vertical alignment film. Furthermore, when a rubbing-treated vertical alignment film is used as the vertical alignment film, the rod-like polymerizable liquid crystal compound is vertically aligned at the air layer interface while being tilted at the vertical alignment film interface. Can do. Therefore, according to the above configuration, an unpolymerized film before polymerization and a polymerized film both produce a film having a small refractive index change in the plane direction of the film and a large refractive index change in the normal direction of the film. be able to.

[0169] Further, as described above, the tilt angle of the refractive index ellipsoid in the optically anisotropic layer can be arbitrarily determined by simply aligning the rod-shaped polymerizable liquid crystal compound with or without rubbing the alignment film for vertical alignment. Can be controlled in the normal direction. Therefore, a film having a desired optical anisotropy can be easily produced.

[0170] As the alignment film for vertical alignment and the rod-like polymerizable liquid crystal compound, those described in <1. Film according to the present invention> can be similarly used. Therefore, among the alignment films for vertical alignment described in <1. Film that works for the present invention>, the rod-shaped polymerizable liquid crystal is not subjected to rubbing treatment in the optically anisotropic layer formed on the vertical alignment film. The compound is nematically aligned vertically to the alignment film for vertical alignment. On the other hand, in the optically anisotropic layer formed on the rubbed vertical alignment film, the rod-like polymerizable liquid crystal compound remains vertically aligned at the air layer interface, and is inclined at the alignment film interface for vertical alignment. Orient. That is, in the optically anisotropic layer formed through the liquid crystal compound-containing composition coating step and the liquid crystal compound-containing composition heating step, the inclination angle of the refractive index ellipsoid in the optically anisotropic layer is arbitrarily set to the normal line. Can be controlled in the direction. Therefore, it is possible to produce a film in which the refractive index change is small in the plane direction of the film and the refractive index change is large in the normal direction of the film.

[0171] Further, in addition to the liquid crystal compound-containing composition coating step and the liquid crystal compound-containing composition heating step, the method for producing a film according to the present invention includes (C) a rod-like polymerizable film that is applied to the vertical alignment film. Step of preparing a composition containing a liquid crystal compound (hereinafter referred to as “liquid crystal Compound-containing composition preparation step “t”), (D) a step of polymerizing an unpolymerized film obtained in the liquid crystal compound-containing composition heating step (hereinafter also referred to as “liquid crystal compound polymerization step”), (E) vertical Including a step of rubbing the alignment film (hereinafter also referred to as “rubbing step”) and (F) a step of forming an alignment film for vertical alignment on the supporting substrate (hereinafter also referred to as “alignment film forming step for vertical alignment”). You may go out. These four steps may all be included, or any one or two of them may be included. Of course, none of them may be included.

[0172] Hereinafter, the alignment film forming process for vertical alignment, the rubbing process, the liquid crystal compound-containing composition preparation process, the liquid crystal compound-containing composition coating process, the liquid crystal compound-containing composition heating process, and the liquid crystal compound polymerization process will be described in detail. .

[0173] (Π— 1) Alignment film formation process for vertical alignment

In the vertical alignment film forming step, a vertical alignment film is formed on the support substrate. The support substrate is not particularly limited. For example, the support substrate exemplified in <1. Film according to the present invention> can be used. The vertical alignment film is not particularly limited. For example, the vertical alignment film shown in <1. Film that can be used in the present invention> can be used. If such an alignment film for vertical alignment is used, it is not necessary to control the refractive index by stretching, so that in-plane variation in birefringence is reduced. Therefore, it is possible to provide a large optical film that can cope with an increase in the size of the FPD on the support substrate.

[0174] The method for forming the alignment film for vertical alignment on the support substrate is not particularly limited, and a conventionally known method can be used. For example, the orientation film for vertical orientation can be formed on the support substrate by applying a material for the orientation film for vertical orientation on the support substrate and then annealing.

[0175] The thickness of the alignment film for vertical alignment thus obtained is not particularly limited, but is preferably 10 nm to 10000 nm, more preferably 10 nm to 1000 nm. Within the above range, the rod-like polymerizable liquid crystal compound can be aligned at a desired angle on the alignment film for vertical alignment in the optically anisotropic layer forming step described later.

[0176] (Π— 2) Rubbing process

In the rubbing process, the vertical alignment film obtained in the alignment film forming process for vertical alignment is Process. As a result, in the liquid crystal compound-containing composition heating step described later, the rod-like polymerizable liquid crystal compound can be tilted at the vertical alignment film interface while maintaining the vertical alignment at the air layer interface. The vertical alignment film is not necessarily obtained in the vertical alignment film forming step, but may be a vertical alignment film having the same physical properties, which is prepared separately, For example, it may be a commercial product.

[0177] The method for rubbing the vertical alignment film is not particularly limited, and a conventionally known method can be used. For example, it is possible to use a method in which a rubbing cloth is wound and a rotating labinder roll is brought into contact with a vertical alignment film which is placed on a stage and conveyed.

[0178] The rubbing cloth is not particularly limited as long as it can be wound around a labinda roll. Examples of the material of the rubbing cloth include various materials such as rayon, cotton, wool and silk. Even with the same material, the rubbing state can be changed depending on the thickness and length of the thread used in the fabric. In order to make the rubbing state uniform, it is preferable that the thickness and length of the thread are uniform.

[0179] The diameter of the labinda roll is generally lOmn in order to stably control its rotation! It is preferably ~ 300mm. Further, by changing the diameter of the rubbing roll, the angle and area of contact with the alignment film can be adjusted.

[0180] Further, the rotation speed of the labinda roll is preferably 100 to 2000 rpm in order to stably rotate the rubbing roll with the force depending on the diameter of the labinda roll. It is also possible to adjust the rubbing force by changing the number of rotations of the labinda roll.

[0181] The stage speed of the above stage and the transport speed of the vertical alignment film are generally difficult to stably transport even if the transport speed of the vertical alignment film is too slow or too fast. It is preferable to control to lmZ minutes to 10 mZ minutes. In addition, the rubbing force can be adjusted by changing the stage speed and the transport speed of the vertical alignment film.

[0182] Further, in the rubbing method exemplified above, the pushing amount and the contact length are not particularly limited, and a desired rubbing effect can be obtained according to the yarn length of the rubbing cloth. It may be set so that. The “push amount” is an amount by which the rubbing roll is pressed against the vertical alignment film, and is expressed by the length of the hair of the rubbing cloth pressed against the alignment film. In the rubbing method described above, it is possible to press the rubbing cloth as much as the thread is perpendicular to the cloth. Further, the “contact length” represents a length where the labinda roll and the substrate are in contact with each other. The contact length can be changed to a length where the labinda roll and the vertical alignment film are in contact with each other when the rubbing roll is completely pressed after the labinda roll contacts the vertical alignment film.

Thus, in the rubbing step, the force for rubbing the vertical alignment film by the method as exemplified above, the number of rubbing times of the vertical alignment film in the rubbing step is not particularly limited. That is, in the rubbing step, the vertical alignment film may be rubbed only once, or may be rubbed multiple times to control the orientation! /.

(II 3) Liquid crystal compound-containing composition preparation step

In the liquid crystal compound-containing composition preparation step, a composition containing a rod-like polymerizable liquid crystal compound is prepared. Specifically, a solution in which the rod-like polymerizable liquid crystal compound is dissolved in an organic solvent is prepared. As the rod-like polymerizable compound, the rod-like polymerizable liquid crystal compound described in (I) Film according to the present invention may be used. The organic solvent is not particularly limited as long as it can dissolve the rod-like polymerizable liquid crystal compound. For example, cyclopentanone, cyclohexanone, methyl ethyl ketone, toluene, ethyl acetate, methyl caffeosolve, butyl cectosolve, isopropyl alcohol, methyl amyl ketone, xylene, acetonitrile, tetrahydrofuran, gamma-butyrolacton, dimethoxyethane, Examples thereof include ethyl acetate, black-form, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether. These organic solvents may be used alone or in combination.

[0185] Further, the concentration of the rod-like polymerizable liquid crystal compound in the composition is not particularly limited, but if the concentration is too low, the optically anisotropic layer becomes too thin. There is a tendency that the optical anisotropy necessary for this is not obtained. On the other hand, if the concentration is too high, the viscosity of the solution of the liquid crystal compound-containing composition tends to be too high, and the coating film thickness tends to be uneven. Therefore, the above concentration is 5 ~ 50wt% Preferably there is. If it is within the above range, the above-described problems will not occur.

[0186] The composition may further contain a specific polymerizable compound and a plurality of liquid crystal compounds different from Z or the rod-like polymerizable liquid crystal compound.

[0187] As the liquid crystal compound, other liquid crystal compounds described in <1.

[0188] The content of the liquid crystal compound may be appropriately determined according to the retardation value required for the obtained film. Specifically, the ratio of the structural unit derived from the liquid crystal compound contained in the composition is adjusted so as to give a desired retardation value, and the retardation value of the obtained optical film is obtained. Based on the result, the content of the structural unit derived from the liquid crystal compound can be determined.

[0189] Usually, the retardation value can be controlled by changing the film thickness. However, it is difficult to control the retardation value when the incident angle is changed, even if the retardation value in the normal direction can be controlled arbitrarily by controlling the film thickness alone. Must be changed. On the other hand, by adding a structural unit derived from the liquid crystal compound, it is possible to arbitrarily adjust the retardation value at any angle other than the retardation value in the normal direction alone. In other words, the shape of the refractive index ellipsoid of the optically anisotropic layer can be arbitrarily controlled by adding a structural unit derived from the liquid crystal compound. However, if too much structural unit derived from the liquid crystal compound is added, the vertical alignment of the present invention may not be obtained. Therefore, for example, the total content of the structural unit derived from the liquid crystal compound and the structural unit derived from the rod-like polymerizable liquid crystal compound is 100 parts by weight, and the content of the structural unit derived from the liquid crystal compound is 5 to 50 parts by weight. It is preferable to do. By setting it as the above content, the shape of the refractive index ellipsoid of the obtained film can be arbitrarily controlled.

[0190] As the polymerizable compound, the polymerizable compound described in <1. Film that Works in the Present Invention> may be used. By including such a polymerizable compound in the composition, a film having arbitrary wavelength dispersion characteristics can be produced.

[0191] The content of the above-mentioned polymerizable compound may be appropriately determined according to the wavelength dispersion characteristic required for the obtained film. Specifically, the upper limit is set so as to give a desired wavelength dispersion characteristic. The ratio of the structural unit derived from the polymerizable compound contained in the composition is adjusted, and the retardation value of the obtained optical film is obtained. Based on the result, the content of the structural unit derived from the polymerizable compound can be determined.

[0192] In general, the film exhibits positive wavelength dispersion without containing the above-mentioned polymerizable compound or containing a small amount of force. On the other hand, by increasing the content of the structural unit derived from the polymerizable compound, the chromatic dispersion characteristic can be arbitrarily adjusted to the normal wavelength dispersion force and the reverse wavelength dispersion. When obtaining a film exhibiting reverse wavelength dispersion, for example, the structural unit derived from the polymerizable compound with respect to a total of 100 parts by weight of the structural unit derived from the polymerizable compound and the structural unit derived from the rod-like polymerizable liquid crystal compound. The content of is preferably 5 to 50 parts by weight. By setting it as the above content, the obtained film can be a film showing a large retardation value at the same time as showing reverse wavelength dispersion.

[0193] Further, in the film production method according to the present invention, the wavelength dispersion characteristics (positive wavelength dispersion to reverse wavelength dispersion) of the obtained film are performed by the composition change of the composition. Therefore, there is an effect that the wavelength dispersion characteristic of the film can be arbitrarily adjusted by a very simple method.

[0194] The composition may contain a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and the like.

[0195] As the polymerization initiator, the polymerization initiators described in (I) Film which is useful in the present invention can be used. The addition amount of the polymerization initiator is an amount suitable for the polymerization reaction of the rod-like polymerizable liquid crystal compound and Z or the polymerizable compound, and disturbs the orientation of the rod-like polymerizable liquid crystal compound. It is enough if it is not. That is, it is preferable to determine appropriately according to the types of the rod-like polymerizable liquid crystal compound, the polymerizable compound, and the polymerization initiator, and the composition of the composition. Thus, the specific value of the addition amount of the polymerization initiator is not particularly limited. For example, 0.1 to 30 parts by weight with respect to 100 parts by weight of the rod-like polymerizable liquid crystal compound. It is more preferably 0.5 to 10 parts by weight. Within the above range, the rod-like polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the rod-like polymerizable liquid crystal compound.

[0196] As the polymerization inhibitor, the polymerization inhibitor described in <1. Can be used. The addition amount of the polymerization inhibitor is not particularly limited, and the rod-like polymerizable liquid crystal compound that does not disturb the orientation of the rod-like polymerizable liquid crystal compound and

Any amount can be used as long as the polymerization reaction of Z or the polymerizable compound can be controlled and the stability of the optically anisotropic layer can be improved. Specifically, it is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the rod-like polymerizable liquid crystal compound. Within the above range, the polymerization of the rod-like polymerizable liquid crystal compound without disturbing the orientation of the rod-like polymerizable liquid crystal compound can be controlled, and the stability of the optically anisotropic layer can be improved.

[0197] Further, as the photosensitizer, the photosensitizer described in <1. Film according to the present invention> can be used. Further, the amount of the photosensitizer added is not particularly limited. The polymerization reaction of the rod-like polymerizable liquid crystal compound and Z or the polymerizable compound that does not disturb the orientation of the rod-like polymerizable liquid crystal compound is not limited. If the amount can be increased sensitivity. Specifically, 0.1 to 30 parts by weight is preferable with respect to 100 parts by weight of the rod-like polymerizable liquid crystal compound, and 0.5 to 10 parts by weight is more preferable. Within the above range, the sensitivity of the polymerization of the rod-like polymerizable liquid crystal compound without disturbing the orientation of the rod-like polymerizable liquid crystal compound can be increased.

[0198] Further, as the leveling agent, the leveling agent described in <I. Film which is useful in the present invention> can be used. Further, the amount of the leveling agent added is not particularly limited, and the optically anisotropic layer that does not disturb the orientation of the rod-like polymerizable liquid crystalline compound is smoothed, or the composition of the liquid crystal compound-containing composition is not limited. Any amount can be used as long as it can control the fluidity during coating or adjust the crosslink density of the rod-like polymerizable liquid crystalline composite. Specifically, 0.1 to 30 parts by weight is preferable with respect to 100 parts by weight of the rod-like polymerizable liquid crystal compound, and 0.5 to 10 parts by weight is more preferable. Within the above range, the optically anisotropic layer that does not disturb the orientation of the rod-like polymerizable liquid crystalline compound is smoothed, or the fluidity at the time of coating the liquid crystal compound-containing composition is controlled. In addition, the crosslink density of the rod-like polymerizable liquid crystalline compound can be adjusted.

[II99] Liquid crystal compound-containing composition coating process

In the liquid crystal compound-containing composition coating step, the liquid crystal compound-containing composition preparation step The prepared composition is applied on the alignment film for vertical alignment. Thereby, the coating film containing the said composition can be formed on the alignment film for vertical alignment. Here, the composition is a composition having an equivalent composition than that prepared in the liquid crystal compound-containing composition preparation step, and a composition containing a separately prepared rod-like polymerizable liquid crystal compound, for example, a commercially available product. May be used.

[0200] The method of applying the composition onto 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 bar coating method, and a spin coating method can be used.

[0201] The coating amount of the composition is not particularly limited, and may be applied in an appropriate amount so as to give a film thickness that gives a desired retardation value to the obtained film. As described above, by adjusting the film thickness, the retardation value (retardation value, Re (D)) of the obtained film can be determined.

[0202] As described above, the thickness of the layer formed by applying the composition varies depending on the retardation value of the obtained film. In the present invention, the thickness is preferably 0.1 to 10 m, and more preferably 0.5 to 2 m. If it is in the said range, it can be set as the retardation value of the film which is effective in this invention mentioned above.

[0203] As described above, in the liquid crystal compound-containing composition coating step, the optically anisotropic layer (liquid crystal layer) is laminated on the alignment film for vertical alignment laminated on an arbitrary supporting substrate. Therefore, the production cost can be reduced as compared with a method of manufacturing a liquid crystal cell and injecting a liquid crystal compound into the liquid crystal cell. Furthermore, it is possible to produce a film using a roll film.

[0204] (II 5) Liquid crystal compound-containing composition heating step

In the liquid crystal compound-containing composition heating step, the coating film formed in the liquid crystal compound-containing composition coating step is heated. Thereby, the solvent contained in the coating film is dried, and an unpolymerized film in which the rod-like polymerizable liquid crystal compound is in an unpolymerized state can be obtained. The unpolymerized film thus obtained is also included in the present invention. The unpolymerized film exhibits a liquid crystal phase such as a nematic phase and has birefringence due to monodomain alignment. Ma The unpolymerized film is usually oriented at a low temperature of about 10 to 120 ° C, preferably 25 to 80 ° C. Therefore, in the present invention, a substrate having low heat resistance can be used as the support substrate described above.

[0205] In the liquid crystal compound-containing composition heating step, the method for heating the composition, the heating conditions, and the like may be any conditions as long as an unpolymerized film having the above physical properties is obtained. Specifically, the heating temperature is preferably 10 to 120 ° C, and more preferably 25 to 80 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. If the heating temperature and the heating time are within the above ranges, a supporting substrate that does not necessarily have sufficient heat resistance can be used as the supporting substrate.

[Π206] (6) Liquid crystal compound polymerization process

In the liquid crystal compound polymerization step, the unpolymerized film obtained in the liquid crystal compound-containing composition heating step is polymerized and cured. As a result, a film in which the orientation of the rod-like polymerizable liquid crystal compound is fixed, that is, a polymerized film is obtained. Therefore, it is possible to produce a polymerized film having a large refractive index change in the normal direction of the film and a small refractive index change in the plane direction of the film.

[0207] The method for polymerizing the unpolymerized film is determined according to the kind of the rod-like polymerizable liquid crystal compound and the polymerizable compound. For example, the unpolymerized film can be polymerized by photopolymerization or thermal polymerization. In the present invention, it is particularly preferable to polymerize the unpolymerized film by photopolymerization. According to this, since the unpolymerized film can be polymerized at a low temperature, the selection range of the heat resistance of the supporting substrate is expanded. In addition, it is easy to manufacture industrially.

[0208] The method for photopolymerizing an 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.

[0209] Thus, 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-like polymerizable liquid crystal compound can be crosslinked by photopolymerization. Therefore, there is an effect that it is not easily affected by the change in birefringence due to heat. Also drooping It is not necessary to use a surface treatment agent such as a surfactant in the alignment film for direct alignment. That is, the alignment film of the film according to the present invention (vertical alignment film) has good adhesion between the support substrate and the alignment film and between the alignment film and the optically anisotropic layer. Is easy to manufacture. Furthermore, according to the method for producing a film according to the present invention, it is possible to produce an optical compensation film having a desired retardation value as a thin film, as compared with a stretched film that is expected to have the same performance. .

[0210] KU III. Use of Film for Powering the Present Invention>

The film covered in the present invention can be widely used as an optical film having excellent wavelength dispersion characteristics. Examples of the optical film include an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptical polarizing film, a viewing angle widening film, and an optical compensation film for compensating a viewing angle of a transmissive liquid crystal display. I can list them.

[0211] Further, the film according to the present invention is also used in a retardation plate of a reflective liquid crystal display and an organic electoluminescence (EL) display, and in a flat panel display device including the retardation plate and the optical film. Can be used. The flat panel display device is not particularly limited, and examples thereof include a liquid crystal display device (LCD) and organic electroluminescence (EL).

[0212] As described above, the film that is useful in the present invention can be used in a wide range of applications. For example, a polarizing film formed by laminating films that are useful for the present invention, and a flat panel display device provided with a film or polarizing film that is useful for the present invention will be described below.

[0213] (III 1) Polarizing film

The embodiment of the polarizing film that works on the present invention will be described below based on FIGS. 3A to 3E. The polarizing film of the present invention is not limited to this.

[0214] The polarizing film useful in the present invention is a film having a polarizing function, that is, obtained by laminating one or both surfaces of the polarizing layer directly or using an adhesive. [0215] For example, as shown in FIGS. 3A to 3E, (1) Embodiment in which film 1 and polarizing layer 2 are directly bonded (FIG. 3A), (2) Film 1 and polarizing layer 2 Is an embodiment in which the film is bonded through the adhesive layer 3 (FIG. 3B), (3) an embodiment in which the film 1 and the film 1 are directly bonded, and further, the film 1 ′ and the polarizing layer 2 are directly bonded. (Fig. 3C), (4) Embodiment in which film 1 and film 1 'are bonded via adhesive layer 3, and further, polarizing layer 2 is bonded directly on film 1' (Fig. 3D), And (5) an embodiment (FIG. 3E) in which film 1 and film 1 ′ are bonded together through adhesive layer 3, and film 1 ′ and polarizing layer 2 are bonded together through adhesive layer 3 ′. Can be mentioned.

For convenience of explanation, the same reference numbers are assigned to the same elements.

In FIG. 3F, the liquid crystal layer 11 is used as the film 1, and the alignment layer 1 is included in the film 1.

2 is not included. The film 1 and the polarizing layer 2 are bonded together via a pair of adhesive layers or adhesive layers 3.

In FIG. 3G, the liquid crystal layer 11 is used as the film 1, and the alignment layer 12 may not be included in the film 1. A pair of films 1 are bonded through an adhesive layer or an adhesive layer 3, and a polarizing layer 2 is bonded to the outside through the adhesive layer or the adhesive layer 3. FIG. 3H shows the same structure as FIG. 3F. However, unlike FIG. 3F, a film 1A includes a support film 13, an 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. A laminated structure is used.

FIG. 31 shows a structure similar to FIG. 3G. However, unlike FIG. 3G, the film 1A includes a support film 13, a laminate including an 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 body (laminated structure) is used.

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

[0216] The polarizing layer 2 is not particularly limited as long as it is a film having a polarizing function. Absent. For example, as the polarizing layer 2, a film obtained by adsorbing iodine or a dichroic dye on a polybulualcohol-based film or a film obtained by stretching a polybulualcohol-based film to adsorb iodine or a dichroic dye is used. be able to.

[0217] The adhesive used for the adhesive layer 3 and the adhesive layer 3 'is not particularly limited, but is preferably an adhesive having high transparency and excellent heat resistance. As such an adhesive, for example, an acrylic, epoxy, or urethane adhesive is used.

[0218] Moreover, in the polarizing film, as shown in Figs. 3C to 3E, the film according to the present invention may be laminated in one to three layers as necessary.

[0219] (III 2) Flat panel display

The flat panel display device which is effective in the present invention is provided with a film or polarizing film which is effective in the present invention. For example, a liquid crystal display device including a liquid crystal panel on which a polarizing film that works on the present invention and a liquid crystal panel are bonded together, or an organic electorium luminescence (on which a light emitting layer is bonded on a polarizing film that covers the present invention) ( An organic EL display device having a panel (hereinafter also referred to as “EL”) can be given.

[0220] As embodiments of the flat panel display device according to the present invention, a liquid crystal display device and an organic EL will be described in detail below, but the present invention is not limited thereto.

[Embodiment 1]

The liquid crystal display device according to Embodiment 1 includes the liquid crystal panel shown in FIG. The liquid crystal panel is obtained by bonding a polarizing film 4 and a liquid crystal panel 6 through an adhesive layer or an adhesive layer 5. According to the above configuration, when a voltage is applied to the liquid crystal panel using an electrode (not shown), the liquid crystal molecules are driven to produce an optical shutter effect.

[Embodiment 2]

The organic EL display device according to the second embodiment includes the organic EL panel shown in FIG. The organic EL panel is obtained by bonding the polarizing film 4 and the light emitting layer 7 through the adhesive layer or the adhesive layer 5.

[0223] In addition to the organic EL panel, the polarizing film 4 functions as a broadband circularly polarizing plate.

The light emitting layer 7 is at least one layer having a conductive organic compound power. Note that the present invention is not limited to the configurations described above, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments respectively. Embodiments obtained by appropriately combining the above are also included in the technical scope of the present invention.

Example

[0225] The present invention will be described more specifically based on Examples and Comparative Examples, and Figs. 6 and 7, but the present invention is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. The wavelength dispersion characteristics in the following examples and comparative examples were performed as follows.

[0226] [Measurement of wavelength dispersion characteristics]

58.5 At a wavelength of 6 nm, the incident angle dependence of the retardation value of the produced film was measured using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments). 6 and 7 show the phase difference value [Re ()] at a wavelength of 585.6 nm when the incident angle is changed with respect to the fast axis. At the same time, the front retardation value Ro (nm) of the produced film was measured at a wavelength of 585.6 nm using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments).

[0227] Also, the incident angle dependence of the retardation value of the manufactured film was measured using a measuring instrument (Spectroscopic Ellipsometer 1: M-220, manufactured by JASCO Corporation), and the direction of the perpendicular axis of the film plane and the film thickness were measured. The refractive indices in the vertical direction were measured as _nx , _ny , and nz, respectively.

[Example 1: Production of vertically oriented film]

A solution for polyimide alignment film for vertical alignment (SE-5300, manufactured by Nissan Chemical Industries, Ltd.) was applied on a glass substrate and then annealed to obtain a 104 nm thick alignment film for vertical alignment. Subsequently, a composition RMS-03-011 (manufactured by Merck & Co., Inc.) containing a rod-like polymerizable liquid crystal compound that is horizontally aligned on a horizontal alignment film without rubbing treatment and aligned vertically at the air interface is spun. It was applied by the coating method and dried at 55 ° C for 1 minute. The obtained unpolymerized film was confirmed to be monodomain by a polarizing microscope. Subsequently, an ultraviolet ray was irradiated to produce a film having a film thickness of 1.2 m. The resulting film was able to be applied evenly without repellency, and had good adhesion without being peeled off when left indoors for 30 days. [0229] The incident angle dependency of the obtained film was measured by the above method. The results are shown in Figure 6 and Table 5. The graph shows that the phase difference value increases as the incident angle to the film increases with an incident angle of 0 °. The tilt angle of this film was shown to be 90 °.

[0230] With respect to the obtained film, the front phase difference value Ro was also measured by the above method, and was found to be On m. From these results, it was found that the inclination angle of the refractive index ellipsoid with respect to the film plane was 90 °.

[0231] [Table 5] Table 5 Analysis results of the rubbing conditions and the incident angle dependence of the film

[Examples 2 to 4: Production of inclined alignment film]

A polyimide alignment film for vertical alignment (SE-5300, manufactured by Nissan Chemical Industries, Ltd.) was applied on a glass substrate and then annealed to obtain a film having a thickness of 104 nm. The alignment film is rubbed once with rayon (YA-20-R, manufactured by Yoshikawa Chemical Industries), followed by rod polymerization that is horizontally aligned on the horizontal alignment film and vertically aligned at the air interface. Composition RM S-03-011 (manufactured by Merck & Co., Inc.) containing a conductive liquid crystal compound was applied by spin coating and dried at 55 ° C. for 1 minute. The obtained unpolymerized film was confirmed to be monodomain by a polarizing microscope. Subsequently, ultraviolet rays were irradiated to polymerize the polymerizable liquid crystal compound, and an optical film having a thickness of 1. was produced. The obtained film was able to be applied uniformly without repellency, and when it was left indoors for 30 days, no peeling was observed, and the adhesion was good.

[0233] The incident angle dependency of the obtained film was measured by the above method. As an example of the results, the results of the film of Example 2 are shown in FIG. 7 and Table 5. The results of Examples 3 and 4 are shown in Table 5. The films of Examples 2 to 4 have an incident angle of 19 respectively. The phase difference value increases as the incident angle to the film is increased, centering around −6 ° and −10 °. I found out that The tilt angles of this film were shown to be 71 °, 84 ° and 80 °, respectively.

[0234] Further, for the obtained optical film, the front phase difference value Ro was also measured by the above method. As a result, the Ros of the films of Examples 2 to 4 were 18 nm, 5 nm, and 9 nm, respectively. From these results, in Examples 2 to 4, it was found from these results that the inclination angles of the refractive index ellipsoid with respect to the film plane were 71 °, 84 °, and 80 °.

[Comparative Example 1]

As a liquid crystal compound-containing composition, a film was produced in the same manner as in Example 1, except that the coating solution shown in Table 6 was used instead of the composition RMS-03-011 (Merck Co., Ltd.). . The obtained unpolymerized film was confirmed not to be monodomain by a polarizing microscope.

[0236] [Table 6] Table 6 Coating solution composition

*: Irgacure 9 0 7 (Ciba Specialty Chemicals) Industrial applicability

[0237] The film that is useful in the present invention is a film that can provide a high refractive index in the normal direction of the film, not in the plane direction of the film. Therefore, the present invention is an optical film having excellent wavelength dispersion characteristics such as an antireflection film such as an anti-reflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, and a viewing angle widening film. Can be used. Furthermore, the present invention can also be used for retardation plates of reflective liquid crystal displays and organic electroluminescence (EL) displays, and flat panel display devices (FPD) equipped with such retardation plates.

Claims

The scope of the claims

[1] A film having an optically anisotropic layer formed on an alignment film for vertical alignment, wherein the optically anisotropic layer contains a polymer containing a structural unit derived from a rod-like polymerizable liquid crystal compound Consist of layers,

The rod-like polymerizable liquid crystal compound has a property of being oriented horizontally on a horizontal alignment film as a monomer and vertically aligned at an air interface,

Refractive indexes in the direction perpendicular to the film plane and in the film thickness direction are _nx

, Ny, nz, satisfying nz> nx and nz> ny

[2] The finolem according to claim 1, wherein the alignment film for vertical alignment is a vertical alignment film.

[3] The tilt angle of the refractive index ellipsoid in the optically anisotropic layer with respect to the film plane is 90

The film according to claim 2, wherein the film is 5 °.

[4] The film according to [1], wherein the alignment film for vertical alignment is an alignment film obtained by rubbing the vertical alignment film.

[5] The inclination angle of the refractive index ellipsoid in the optically anisotropic layer with respect to the film plane is 45 °.

5. The film according to claim 4, wherein the film is -85 [deg.].

[6] A film having an optically anisotropic layer formed on an alignment film for vertical alignment, the optically anisotropic layer comprising a layer containing a rod-like polymerizable liquid crystal compound, and the rod-like polymerizable liquid crystal The compound has the property of being oriented horizontally on the horizontally oriented film and vertically oriented at the air interface,

, Ny, nz, satisfying nz> nx and nz> ny

[7] The film according to any one of [1] to [6], which exhibits reverse wavelength dispersion.

[8] The optically anisotropic layer has the following formula (1):

[Chemical 1] P2-E2-X2-B2-A2- (G2) t— Y— (Gl) s A 1— B 1— X 1— E 1— F 1 (1)

(Wherein Y represents a divalent group, s and t each independently represent an integer of 0 or 1, G 1 and G2 each independently represent — CR ¹ ! ^, R ¹ and R ² each independently represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, or a hydrogen atom,

A1 and A2 each independently represent a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylenephenylene group, an oxyphenylene group, or a thiophenylene group, and A1 and A2 each have An alkyl group of 1 to 5, an alkoxy group of 1 to 5 carbon atoms, or a halogen atom may be bonded, and B1 and B2 are each independently -CRR 'C≡C CH = CH

-CH -CH O S C (= 0) C (= 0) — O

twenty two

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 (→ 0) = N N = N (→ 0) C (= 0) — NR

NR— C (= 0) -OCH NR CH O SCH

2 2 2

-CH S—, -CH = CH-C (= 0) O O— C (= 0) — CH = CH—, single connection

2

Represents a divalent group selected as a combined force, R and R ′ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and XI and X2 each independently represent the following formula (2 )

[Chemical 2]

(Wherein A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, B3 has the same meaning as B1 and B2, and n represents an integer of 1 to 4)

E1 and E2 each independently represents an alkylene group having 2 to 25 carbon atoms, E1 and E2 are further an alkyl group having 1 to 5 carbon atoms, 1 carbon atom ~ 5 alkoxy groups, halogen atoms may be bonded PI and P2 represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is a polymerizable group. )

The film according to claim 7, comprising a polymer containing a structural unit derived from a polymerizable compound represented by the formula:

[9] A method for producing a film having an optically anisotropic layer formed on an alignment film for vertical alignment,

(A) applying a composition containing a rod-like polymerizable liquid crystal compound on an alignment film for vertical alignment;

(B) at least a step of calorie heating the coating film formed in the step (A) at 25 ° C. to 120 ° C. for 10 seconds to 60 minutes,

A method for producing a film, wherein the rod-like polymerizable liquid crystal compound has a property of being oriented horizontally as a monomer on a horizontally oriented film and vertically oriented at an air interface.

[10] The method for producing a film according to [9], further comprising the step of (C) crosslinking the rod-like liquid crystal compound by photopolymerization.

[11] A polarization vinylome obtained by laminating the film according to any one of claims 1 to 8.

[12] A flat panel display comprising the film according to any one of claims 1 to 8, or the polarizing film according to claim 11.

[13] An optically anisotropic layer made of liquid crystal, the optically anisotropic layer having a first surface and a second surface parallel to the first surface;

An alignment layer in contact with the first surface of the optically anisotropic layer;

A film comprising

The liquid crystal located in the vicinity of the first surface of the optically anisotropic layer is oriented almost horizontally, and the liquid crystal located in the vicinity of the second surface of the optically anisotropic layer is oriented almost vertically,

First refractive index (nz) in the first direction perpendicular to the film, second refractive index (nx) in the second direction perpendicular to the first direction of the film, and perpendicular to the first and second directions of the film In the third refractive index (nx) in the third direction, the first refractive index (nz) is the second refractive index (nx) and the third refractive index (nz). Larger, film,