JP2007233376A - Liquid crystal display device having patterned color filter layer and optical anisotropic layer, method for manufacturing the device, and color filter substrate and method for manufacturing the substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal display device in which a liquid crystal cell can be optically compensated accurately, having excellent productivity and improved angle-of-view property of color. <P>SOLUTION: The liquid crystal display device has a liquid crystal (31) held between a first substrate and a second substrate (21), and the device is characterized in that: the first substrate (21) has a patterned layer divided into fine areas; the patterned layer contains a color filter layer (23) and an optical anisotropic layer (27) laminated in the direction of the normal line of the substrate; and a barrier wall (22) is disposed at a boundary portion of the patterned layers. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal display device having a patterned color filter layer and an optically anisotropic layer on the surface of a substrate such as a liquid crystal cell, and a method for manufacturing the same.

  CRT (Cathode Ray Tube) has been mainly used as a display device used for OA devices such as word processors, notebook personal computers, personal computer monitors, portable terminals, and televisions. In recent years, liquid crystal display devices (LCDs) have been widely used instead of CRTs because of their thinness, light weight, and low power consumption. The liquid crystal display device has a liquid crystal cell and a polarizing plate. The polarizing plate is composed of a protective film and a polarizing film, and is obtained by dyeing a polarizing film made of a polyvinyl alcohol film with iodine, stretching, and laminating both surfaces with a protective film. For example, in a transmissive LCD, this polarizing plate is attached to both sides of a liquid crystal cell, and one or more optical compensation sheets may be disposed. On the other hand, in a reflective LCD, a reflector, a liquid crystal cell, one or more optical compensation sheets, and a polarizing plate are arranged in this order. The liquid crystal cell includes a liquid crystal molecule, two substrates for encapsulating the liquid crystal molecule, and an electrode layer for applying a voltage to the liquid crystal molecule. The liquid crystal cell performs ON / OFF display depending on the alignment state of liquid crystal molecules, and can be applied to any of a transmissive type, a reflective type, and a semi-transmissive type, such as TN (Twisted Nematic), IPS (In-Plane Switching), Display modes such as OCB (Optically Compensatory Bend), VA (Vertically Aligned), ECB (Electrically Controlled Birefringence), and STN (Super Twisted Nematic) are proposed. However, the color and contrast that can be displayed on a conventional LCD vary depending on the angle at which the LCD is viewed. Therefore, the viewing angle characteristic of LCD does not reach the performance of CRT.

  In order to improve the viewing angle characteristics, a viewing angle compensation phase difference plate (optical compensation sheet) has been applied. Until now, LCDs having excellent contrast viewing angle characteristics have been proposed by using optical compensation sheets having various optical characteristics for the various display modes described above. In particular, the three modes OCB, VA, and IPS have wide viewing angle characteristics in all directions as wide viewing angle modes, and are already widely used in homes as television applications. A display has also appeared.

  In a large-size LCD, there is a problem of so-called corner unevenness in which light leakage occurs at the corner of the LCD due to a change in size of the polarizing plate due to environmental humidity. In particular, when the optical compensation sheet is bonded to the polarizing plate directly or via an adhesive layer, the corner unevenness deteriorates due to the change in the optical characteristics of the viewing angle compensation layer having a large retardation change depending on the size.

  Further, the method using the optical compensation sheet can effectively improve the contrast viewing angle characteristics, but the improvement effect is not sufficient for the color viewing angle characteristics, and the improvement of the color viewing angle characteristics is an important issue for LCDs. The color viewing angle characteristic of the LCD is derived from the fact that the wavelength changes in three typical colors of R, G, and B, so that the change due to the phase difference of the polarization is different even with the same phase difference. In order to optimize this, the wavelength dependence of the birefringence of the optically anisotropic material, that is, the birefringence wavelength dispersion is optimized with respect to R, G, and B. In the current LCD, since the birefringence wavelength dispersion of liquid crystal molecules used for ON / OFF display and the birefringence wavelength dispersion of the optical compensation sheet cannot be easily controlled, the color viewing angle characteristics have not been improved sufficiently.

  A phase difference plate using a modified polycarbonate has been proposed as an optical compensation sheet in which birefringence wavelength dispersion is controlled for color viewing angle characteristics (Patent Document 1). By using this for a λ / 4 plate in a reflective liquid crystal display device or an optical compensation sheet in the VA mode, the color viewing angle characteristics can be improved. However, the modified polycarbonate film is not yet widely used for LCDs because not only the raw material itself is expensive, but also non-uniformity in optical properties such as bowing occurs in stretching used in the production process.

  On the other hand, although the principle is the same as the contrast viewing angle compensation by the optical compensation sheet, a method for independently compensating for the three colors of R, G, and B has also been proposed (Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7). This is mainly realized by a method of patterning a retardation plate together with a color filter or the like in a liquid crystal cell. However, in order to pattern the retardation plate in the liquid crystal cell, for example, in the cell, formation of an alignment film layer, rubbing treatment, application of a polymerizable liquid crystal composition, alignment, fixation, formation of a resist layer, etching It is difficult to form an optically anisotropic layer having optically uniform retardation characteristics because it requires complicated operations such as processing and stripping and removing the resist layer. In addition, there is a problem that the retardation of the retardation plate changes before and after the etching due to heat and photoresist solvent generated when forming the resist pattern.

On the other hand, an inkjet method is known as a method for producing a color filter. The ink jet method ejects ink while moving the ink jet head on a transparent substrate and directly forms a pattern, and thus does not require exposure and development processes. For this reason, the ink jet method can reduce the cost by reducing the amount of ink used and simplifying the process, and is currently attracting attention as a color filter manufacturing method. It has also been proposed to use the above-described ink jet method for the production of an optically anisotropic layer (Patent Document 8).
JP 2004-37837 A GB2394718 JP 2004-240102 A Japanese Patent Laying-Open No. 2005-4124 JP 2005-24919 A JP 2005-24920 A JP 2006-78647 A JP 2006-64858 A

  An object of the present invention is to provide a color filter substrate having precise pattern-like optical anisotropy, and a simple and stable manufacturing method of such a color filter substrate. The present invention also provides a liquid crystal display device in which the liquid crystal cell is accurately optically compensated, has excellent productivity, and has improved color viewing angle characteristics, and a simple and stable method for manufacturing such a liquid crystal display device. The task is to do.

(1) A liquid crystal display device in which liquid crystal is sandwiched between a first substrate and a second substrate, wherein the first substrate has a pattern layer patterned in a fine region, and the pattern layer is A liquid crystal display device comprising a color filter layer and a first optically anisotropic layer laminated in a normal direction of the substrate, and a partition wall formed at a boundary portion of each pattern layer.
(2) The liquid crystal display device according to (1), wherein the fine regions are arranged in a matrix.
(3) The optically anisotropic layer is a layer fixed by irradiation with heat or ionizing radiation after applying and drying a fluid containing a liquid crystal compound having at least one reactive group to form a liquid crystal phase. A liquid crystal display device according to (1) or (2).
(4) The liquid crystal display device according to (3), wherein the ionizing radiation is ultraviolet rays.
(5) The liquid crystal display device according to (3) or (4), wherein the reactive group is an ethylenically unsaturated group.
(6) The liquid crystal display device according to any one of (3) to (5), wherein the fluid further contains at least one radical polymerization initiator.
(7) The liquid crystal display device according to any one of (3) to (6), wherein the liquid crystalline compound is a rod-like liquid crystal.

(8) The liquid crystal display device according to (7), wherein the rod-like liquid crystal exhibits a smectic A phase.
(9) The liquid crystal of (7) in which the rod-like liquid crystal exhibits a nematic phase or a smectic A phase, and the intrinsic birefringence Δn (λ) at the wavelength λ of the liquid crystal phase satisfies the following formulas (I) and (II): Display device:
Formula (I): Δn (450 nm) / Δn (550 nm) <1
Formula (II): Δn (650 nm) / Δn (550 nm)> 1.
(10) The liquid crystal display device according to any one of (3) to (6), wherein the liquid crystal compound is a discotic liquid crystal compound.
(11) The liquid crystal display device according to any one of (3) to (6), wherein the first optically anisotropic layer contains molecules of a discotic liquid crystalline compound fixed in a substantially vertical alignment state.
(12) The liquid crystal display device according to any one of (3) to (7), wherein the liquid crystal phase is a cholesteric phase.
(13) The in-plane retardation (Re) of the first optical anisotropic layer is not 0, and the first optical anisotropic layer has an in-plane slow axis as a tilt axis (rotation axis). The retardation value measured by making light of wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the layer surface, and the in-plane slow axis as the inclination axis (rotation axis) with respect to the normal direction of the layer surface The liquid crystal display device according to any one of (1) to (12), wherein the retardation value measured by making light having a wavelength λ nm incident from a direction inclined by -40 ° is substantially equal.
(14) The in-plane retardation (Re) of the first optically anisotropic layer is 15 to 200 nm, the in-plane slow axis is the tilt axis (rotation axis), and the tilt is + 40 ° with respect to the normal direction of the layer surface. The light having the wavelength λ nm from the direction inclined by −40 ° with respect to the normal direction of the layer surface, with the retardation value measured by making the light having the wavelength λ nm incident from the inclined direction and the in-plane slow axis as the tilt axis (rotation axis) The liquid crystal display device according to any one of (1) to (13), wherein the retardation values measured by making the light incident are substantially equal and the values are 50 to 250 nm.
(15) The liquid crystal display device according to any one of (1) to (14), wherein the optically anisotropic layer is formed on a rubbing treatment surface of an alignment layer.
(16) The liquid crystal display device according to any one of (1) to (15), wherein the liquid crystal display device has a second optical anisotropic layer composed of one layer continuous with the first substrate or the second substrate.
(17) The liquid crystal display according to (16), wherein the first optical anisotropic layer is a positive A plate, the second optical anisotropic layer is a negative C plate, and the display mode is a VA mode. apparatus.
(18) The color filter layer includes an R region, a G region, and a B region, and an in-plane letter of the region of the first optical anisotropic layer disposed on or below the R, G, and B regions, respectively. The liquid crystal according to (17), wherein Re (R layer)> Re (G layer)> Re (B layer) is satisfied when the foundation is Re (R layer), Re (G layer), and Re (B layer). Display device.
(19) The liquid crystal display according to (16), wherein the first optical anisotropic layer is a positive C plate, the second optical anisotropic layer is a positive A plate, and the display mode is an IPS mode. apparatus.
(20) The liquid crystal display device of (19), wherein the retardation Re (λ) at the wavelength λ of the positive A-plate satisfies the following formulas (III) and (IV):
(III): Re (450 nm) / Re (550 nm) <1
(IV): Re (650 nm) / Re (550 nm)> 1.
(21) The first optically anisotropic layer is a positive C plate, the in-plane retardation (Re) of the second optically anisotropic layer is not 0, and the in-plane slow axis is inclined. The layer surface with the retardation value measured by making light of wavelength λ nm incident from the direction inclined + 40 ° with respect to the normal direction of the layer surface as the axis (rotation axis), and the in-plane slow axis as the inclination axis (rotation axis) The liquid crystal according to (16), in which the retardation value measured by making light having a wavelength of λ nm incident from a direction inclined by −40 ° with respect to the normal direction is substantially equal, and the display mode is the IPS mode. Display device.
(22) The retardation Re (λ) at a wavelength λ nm of the second optically anisotropic layer region is 20 nm to 150 nm, the in-plane refractive indexes nx and ny (nx> ny), and the thickness direction The Nz value at a wavelength of 550 nm of the second optical anisotropic layer region defined by Nz = (nx−nz) / (nx−ny) using the refractive index nz is 1.5 to 7 (16) or (21) Liquid crystal display device.

(23) The method of manufacturing a liquid crystal display device according to any one of (1) to (22), which includes at least the following steps [1] to [4] in this order:
[1] A step of forming a plurality of partition walls on the surface of the first substrate and forming fine regions separated by the partition walls,
[2] A fluid containing at least one liquid crystalline compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet type discharge head to the fine region at a predetermined position and dried to form a liquid crystal phase. A step of exposing to form an optically anisotropic layer;
[3] A step of laminating a color filter layer on the optically anisotropic layer by ejecting and drying a color filter ink liquid from an ink jet type ejection head;
[4] A step of bonding the first substrate and the second substrate together.
(24) The method for manufacturing a liquid crystal display device according to any one of (1) to (22), which includes at least the following steps [1] to [4] in this order:
[1] A step of forming a plurality of partition walls on the surface of the first substrate and forming fine regions separated by the partition walls,
[2] A step of forming a color filter layer by discharging and drying a color filter ink liquid from an inkjet discharge head to the fine region at a predetermined position;
[3] On the color filter layer, a fluid containing at least one liquid crystal compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet discharge head and dried to form a liquid crystal phase. Then, exposing and laminating an optically anisotropic layer,
[4] A step of bonding the first substrate and the second substrate together.
(25) A step of forming an alignment layer and rubbing the surface of the layer before the step of discharging the fluid containing the at least one liquid crystal compound and exhibiting a predetermined optical anisotropy is included. The method of (23) or (24).
(26) A pattern layer patterned in a fine region on a substrate, the pattern layer including a color filter layer and an optically anisotropic layer laminated in a normal direction of the substrate, and a boundary portion of each pattern layer A color filter substrate, wherein a partition wall is formed on the substrate.
(27) The color filter substrate according to (26), comprising a color filter layer and an optically anisotropic layer in this order on the substrate.
(28) The color filter substrate according to (26), comprising an optically anisotropic layer and a color filter layer in this order on the substrate.
(29) A method for producing a color filter substrate including at least the following steps [1] to [3] in this order:
[1] A step of forming a plurality of partitions on the surface of the substrate and forming a fine region separated by the partitions,
[2] A fluid containing at least one liquid crystalline compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet type discharge head to the fine region at a predetermined position and dried to form a liquid crystal phase. A step of exposing to form an optically anisotropic layer;
[3] A step of laminating a color filter layer on the optically anisotropic layer by discharging and drying a color filter ink liquid from an inkjet discharge head.
(30) Color filter substrate manufacturing method including at least the following steps [1] to [3] in this order:
[1] A step of forming a plurality of partition walls on the surface of the first substrate and forming fine regions separated by the partition walls,
[2] A step of forming a color filter layer by discharging and drying a color filter ink liquid from an inkjet discharge head to the fine region at a predetermined position;
[3] On the color filter layer, a fluid containing at least one liquid crystal compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet discharge head and dried to form a liquid crystal phase. Then, the process of exposing and laminating | stacking an optically anisotropic layer.

  By using the liquid crystal display device of the present invention, the liquid crystal cell can be optically compensated for each color. The liquid crystal display device manufactured by the manufacturing method using the inkjet system of the present invention has a laminate of a patterned color filter and an optically anisotropic layer, and has improved viewing angle characteristics, particularly color viewing angle characteristics. The In addition, according to the present invention, a color filter substrate having precise pattern-like optical anisotropy can be simply provided by using an ink jet method.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is the Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis). The light is incident at a wavelength of λ nm in 10 degree steps from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis). KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value. In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative. In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the case where there is no slow axis, the arbitrary direction in the film plane is the rotation axis), Rth can also be calculated from the following formula (1) and formula (2) based on the value, the assumed value of the average refractive index, and the input film thickness value.

注記：
上記のＲｅ（θ）は法線方向から角度θ傾斜した方向におけるレターデーション値をあらわす。
式におけるｎｘは面内における遅相軸方向の屈折率を表し、ｎｙは面内においてｎｘに直交する方向の屈折率を表し、ｎｚはｎｘ及びｎｙに直交する方向の屈折率を表す。ｄは膜厚を表す。

Note:
The above Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In the equation, nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents a film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is the above-mentioned Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) from −50 degrees to +50 degrees with respect to the film normal direction. The light of wavelength λ nm is incident from each inclined direction in 10 degree steps and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated. In the above measurement, the assumed value of the average refractive index may be a value in a polymer handbook (John Wiley & Sons, Inc.) or a catalog of various optical films. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index values of main optical films are given below:
Cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).
The KOBRA 21ADH or WR calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

The sign of Rth is the case where the phase difference measured when light having a wavelength of 550 nm is incident from a direction inclined + 20 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) exceeds Re. Is positive and negative is below Re. However, in the sample with | Rth / Re | of 9 or more, it was tilted by + 40 ° with respect to the film normal direction with the in-plane fast axis as the tilt axis (rotation axis) using a polarizing microscope with a free rotation base. In the state, the case where the slow axis of the sample which can be determined using the polarizing plate inspection plate is parallel to the film plane is positive, and the case where the slow axis is in the thickness direction of the film is negative.
In the present specification, λ refers to 611 ± 5 nm, 545 ± 5 nm, 435 ± 5 nm for R, G, and B, respectively, and refers to 545 ± 5 nm or 590 ± 5 nm unless otherwise specified.

  In this specification, “substantially” for the angle means that the error from the exact angle is within a range of less than ± 5 °. Furthermore, the error from the exact angle is preferably less than 4 °, more preferably less than 3 °. With regard to retardation, “substantially” means that the retardation is within ± 5%. Further, “Re is not 0” means that the absolute value of Re is 5 nm or more. In addition, the measurement wavelength of the refractive index indicates an arbitrary wavelength in the visible light region unless otherwise specified. In the present specification, “visible light” refers to light having a wavelength of 400 to 700 nm.

[Method for manufacturing liquid crystal display device]
First, an example of the manufacturing method of the liquid crystal display device of this invention is demonstrated using FIG.
A negative black matrix resist material is used on a transparent substrate 11 made of glass or the like, and a black matrix 12 (partition) of a dot pattern is formed using a photolithography method, and a plurality of fine regions a separated by the partition 12 are formed. (FIG. 1A). In the formation of the black matrix 12, there are no particular limitations on the black matrix forming material and the forming process, and there is no problem as long as a black matrix pattern can be formed even by a method other than a method using a photolithography method using a resist material. . The pattern of the black matrix 12 is not limited to the dot pattern, and the arrangement of the color filters to be formed is not particularly limited, and may be any of dot arrangement, stripe arrangement, mosaic arrangement, delta arrangement, and the like.

  The black matrix 12 is preferably subjected to plasma treatment with a gas containing F atoms (CF 4 or the like) after pattern formation, and the surface thereof is subjected to ink repellent treatment. In addition to the plasma treatment, the black matrix 12 may be made to contain an ink repellant in the black matrix material, or the black matrix may be formed from a material that exhibits ink repellency with respect to the glass substrate 11. May be.

  Next, a fluid 13 ′ such as a solution exhibiting a predetermined optical anisotropy is ejected to a fine region a separated by a black matrix 12 that has been subjected to ink repellent treatment if desired, using an ink jet device, thereby producing a fine region. A layer made of the fluid (FIG. 1B) is formed in a. The fluid preferably contains at least one liquid crystalline compound, and is preferably prepared so as to form a liquid crystal phase after drying. A dispersion liquid in which a part or all of a material such as a liquid crystal compound is dispersed may be used as long as it can be ejected by ink jetting, but a solution is preferable. After the ejection of the solution is completed, the solution layer is dried to form a liquid crystal phase and exposed to form the first optical anisotropic layer 13 (FIG. 1C). In order to form a liquid crystal phase, it may be heated as desired, and in that case, a heating device may be used.

  On the first optically anisotropic layer 13 formed in this way, a second ink is ejected with the color filter ink liquid 14 '(FIG. 1 (d)), this is dried, and desired The second color filter layer 14 is formed by exposure or the like ((e)).

  There are no particular restrictions on the ejection conditions of the ink or the like when forming the optically anisotropic layer 13 and the color filter layer 14, but the viscosity of the fluid for forming the optically anisotropic layer or the ink for forming the color filter layer is high. In view of ejection stability, it is preferable to eject the ink with a reduced viscosity at room temperature or under heating (for example, 20 to 70 ° C.). It is preferable to keep the temperature of the ink or the like as constant as possible because fluctuations in the viscosity of the ink or the like greatly affect the droplet size and droplet ejection speed as they are and cause image quality degradation.

  The ink jet head used in the method of the present invention (hereinafter also simply referred to as a head) is not particularly limited, and various known ones can be used. Continuous type and dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the composition can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of injection is 5 to 25 mPa · s, and to control the composition temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

  The optically anisotropic layer 13 and the color filter layer 14 may be stacked in a different order, that is, the optically anisotropic layer 13 may be stacked on the color filter layer 14. Good. Such an embodiment can be produced by changing the order of the step of forming the optically anisotropic layer 13 and the step of forming the color filter layer 14 in the above manufacturing method example.

  In addition, before the step of discharging a fluid expressing optical anisotropy, after applying and drying a material such as polyvinyl alcohol or soluble polyimide to be an alignment film, if necessary, alignment treatment such as rubbing is performed on the surface. May be applied to form an alignment layer, and the solution or the like may be discharged onto the rubbing surface to form an optically anisotropic layer. The alignment layer may be formed by using an ink jet method similarly to the optically anisotropic layer, or may be formed by another method.

  The optical anisotropy layer 13 may be formed using fluids such as the same type of solution, and has an optimal optical anisotropy depending on the hue of the color filter layer 14 formed thereon. It may be formed using fluids such as solutions containing different materials and / or different blending amounts so as to express. In the case of using different solutions depending on the hue of the color filter layer when forming the optically anisotropic layer 13, after discharging all the respective solutions, drying may be performed at the same time. A drying process may be performed. Further, when forming the color filter layer 14, for example, after all ink liquids for forming the R layer, the G layer, and the B layer are ejected, drying may be performed at the same time. A drying process may be performed. Further, the color of the color filter is not necessarily limited to the three colors of red, green, and blue, and may be a multi-primary color filter.

  In this way, the fluid prepared to develop a predetermined optical anisotropy for each region separated by the black matrix 12 corresponding to each pixel of the first substrate, and R, G, and B After the ink liquid was discharged and dried to form an optically anisotropic layer and a color filter layer, the first substrate and the second substrate were bonded together. Before the bonding, a transparent electrode layer and / or an alignment layer may be formed on the color filter layer 14. For example, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by overlapping colored resin compositions forming a color filter, a transparent electrode is formed thereon, and further required Accordingly, it is preferable from the viewpoint of cost reduction that the spacers are formed by overlapping the protrusions for split orientation.

  A liquid crystal cell may be manufactured by injecting a liquid crystal material into a space between the opposing surfaces of the first substrate and the second substrate to form a liquid crystal layer. The first substrate is preferably arranged with the surface on which the optically anisotropic layer and the color filter layer are formed facing inward, that is, facing the surface. Thereafter, a polarizing plate, an optical compensation film, and the like can be attached to the outer surfaces of both substrates, respectively, to produce a liquid crystal display device.

  In the manufacturing method of the present invention, when the fluid for forming the optically anisotropic layer and the ink liquid for forming the color filter layer are disposed at predetermined positions, a black matrix as a partition is formed, and then an inkjet method is used. Therefore, the optically anisotropic layer and the color filter layer can be accurately formed in a predetermined region on the first substrate. Therefore, it can be manufactured with a small number of steps without complicating the structure.

  In the method of the present invention, an example in which an optically anisotropic layer and a color filter layer are formed in each fine region by using ink ejection by an ink jet method has been described. Of course, the invention is not limited to the produced embodiment, and the production method of the optically anisotropic layer and / or the color filter layer is formed by using, for example, a printing method other than the inkjet method. .

[substrate]
At least one of the pair of substrates included in the liquid crystal display device of the present invention has a laminate of a patterned optically anisotropic layer and a color filter layer for compensating the viewing angle of the liquid crystal cell. Furthermore, the optically anisotropic layer has optical characteristics that are optimal for compensating the viewing angle of the liquid crystal cell, depending on the hue of the color filter layer disposed below or above it (for example, for each of R, G, and B colors). It is preferable to have. Such a substrate may be used for either one of the pair of substrates of the liquid crystal cell, or may be used for both. The material of the substrate is not particularly limited as long as it is transparent, but it is desirable that the birefringence is small, and glass, a low birefringence polymer, or the like is used.

FIG. 2 shows a schematic cross-sectional view of an example of a substrate that can be used in the liquid crystal display device of the present invention.
The liquid crystal cell substrate shown in FIG. 2A has a pattern-like shape in which a black matrix 22 is formed as a partition on a transparent substrate 21 and is ejected by an inkjet method into a fine region separated by the partition. A color filter layer 23 and an optically anisotropic layer 27 are formed. Furthermore, a transparent electrode layer 25 and an alignment layer 26 are provided thereon. FIG. 2 shows an embodiment in which the color filter layers 23 of R, G, and B are formed, but as is often seen recently, a color filter layer composed of layers of R, G, B, and W (white) is formed. May be. The first optical anisotropic layer 27 is divided into r, g, and b regions, and has optimum retardation characteristics for the hues of the R, G, and B filter layers 23, respectively.

  Furthermore, as shown in FIG. 2B, the optically anisotropic layer may be divided into a second optically anisotropic layer 24 and a patterned optically anisotropic layer 27. In the case of dividing into two, the solid optical anisotropic layer 24 may be formed on the same color filter side substrate side as the patterned optical anisotropic layer 27, or it is formed on the counter substrate side although not shown. May be. In general, a drive electrode such as a TFT array is generally arranged on the counter substrate side, and may be formed at any position on the counter substrate. However, in the case of an active drive type having a TFT, optical anisotropy is provided. The heat resistance of the conductive layer is preferably higher than that of the silicon layer.

[Liquid Crystal Display]
FIG. 3 is a schematic cross-sectional view of an example of the liquid crystal display device of the present invention.
3 (a) and 3 (b) use the substrates of FIGS. 2 (a) and 2 (b) as upper substrates, respectively, and a glass substrate 21 having a transparent electrode layer 25 with TFT 32 and an alignment layer 26 thereon. Is a liquid crystal display device having a liquid crystal cell 37 with a liquid crystal 31 interposed therebetween. On both sides of the liquid crystal cell 37, a polarizing plate 36 made of a polarizing layer 33 sandwiched between protective layers 34 and 35 made of a cellulose acetate (TAC) film or the like is disposed. The protective layer 35 on the liquid crystal cell side may be a polymer film such as a TAC film that satisfies the optical characteristics as an optical compensation sheet, or may be made of the same polymer film as the protective layer 34. Although not shown in the drawing, in the aspect of the reflective liquid crystal display device, only one polarizing plate is required on the observation side, and a reflective film is provided on the back surface of the liquid crystal cell or on the inner surface of the lower substrate of the liquid crystal cell. Of course, a front light can be provided on the liquid crystal cell observation side. Further, a transflective type in which a transmissive portion and a reflective portion are provided in one pixel of the display device is also possible. The display mode of the present liquid crystal display device is not particularly limited, and can be used for all transmissive and reflective liquid crystal display devices. In particular, the present invention is effective for the VA mode and the IPS mode where color viewing angle characteristics are desired to be improved.

  Hereinafter, although this aspect demonstrates in detail about the material used for preparation, a preparation method, etc., this invention is not limited to this aspect. Other embodiments can also be produced with reference to the following description and conventionally known methods.

[substrate]
In the liquid crystal display device of the present invention, the substrate having the optically anisotropic layer and the color filter layer is not particularly limited, and substrates made of various materials conventionally used as substrates for liquid crystal cells can be used. For example, a metallic support, a metal bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred are transparent glass and synthetic resin film having good dimensional stability.

[First optically anisotropic layer]
In the present invention, the optically anisotropic layer of the substrate is not particularly limited as long as the optically anisotropic layer has optical characteristics that are not isotropic when there is at least one incident direction where Re is not 0 when the phase difference is measured. Although it is not used, it is formed by curing a composition containing at least one liquid crystalline compound into a liquid crystal phase and then irradiating with ultraviolet rays from the viewpoint of easy control of optical properties used in a liquid crystal cell. An optically anisotropic layer is desirable. Moreover, in order to harden | cure by ultraviolet irradiation, it is preferable that the said composition contains a radical polymerization initiator and / or a cationic polymerization initiator. The compound containing a polymerizable group having reactivity with the polymerization initiator itself has liquid crystallinity, or does not impair the liquid crystallinity of the liquid crystalline compound that forms an optically anisotropic layer upon addition. It is preferable that it is an added amount that is not impaired. The addition amount is preferably 0.1 to 50% by weight, more preferably 1.0 to 30% by weight, based on the solid content of the coating solution.

  In the present invention, the optically anisotropic layer functions as an optically anisotropic layer for compensating the viewing angle of the liquid crystal cell as described above. Of course, the optically anisotropic layer alone may have sufficient viewing angle compensation ability, or may be an embodiment satisfying optical characteristics required for viewing angle compensation in combination with other layers. The optically anisotropic layer is preferably formed from a composition containing at least one liquid crystalline compound. Moreover, when utilizing the manufacturing method of this invention, the said optically anisotropic layer contains at least 1 type of liquid crystalline compound, and is formed from the fluid which expresses optical anisotropy. The fluid may be a liquid crystal compound solution or a dispersion, but is preferably a solution.

  In general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type based on their shapes. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In this embodiment, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. It is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group, since at least one of the reactive groups in one liquid crystal molecule can be formed. Is more preferably 2 or more. The liquid crystalline compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups. The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

  Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. The polymer liquid crystalline compound is a polymer compound obtained by polymerizing a rod-like liquid crystalline compound having a low molecular reactive group. The rod-like liquid crystal compound having a low-molecular reactive group that is particularly preferably used is a rod-like liquid crystal compound represented by the following general formula (I).

Formula (I): Q ¹ -L ¹ -A ¹ -L ³ -ML ⁴ -A ² -L ² -Q ²
Wherein, Q ¹ and Q ² respectively represent a reactive group, the L ^1, L ^2, L ³ and L ⁴ respectively represent a single bond or a divalent linking group, L ³ and At least one of L ⁴ is preferably —O— or O—CO—O—. A ¹ and A ² each independently represent a spacer group having 2 to 20 carbon atoms. M represents a mesogenic group.

Hereinafter, the rod-like liquid crystal compound having a reactive group represented by the general formula (I) will be described in more detail. In the formula, Q ¹ and Q ² are each independently a reactive group. The polymerization reaction of the reactive group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the reactive group is preferably a reactive group capable of an addition polymerization reaction or a condensation polymerization reaction. Examples of reactive groups are shown below.

Examples of the divalent linking group represented by L ¹ , L ² , L ³ and L ⁴ include —O—, —S—, —CO—, —NR ² —, —CO—O—, and —O—CO. —O—, —CO—NR ² —, —NR ² —CO—, —O—CO—, —O—CO—NR ² —, —NR ² —CO—O—, and NR ² —CO—NR ^2. A divalent linking group selected from the group consisting of-is preferred. R ² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In this case, at least one of L ³ and L ⁴ is preferably —O— or O—CO—O— (carbonate group). In the formula (I), Q ¹ -L ¹ and Q ² -L ² -are CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O—, and CH ₂ ═C ( Cl) -CO-O-CO- O- are _{preferable, CH 2 = CH-CO-} O- is most preferable.

A ¹ and A ² represent spacer groups having 2 to 20 carbon atoms. An aliphatic group having 2 to 12 carbon atoms is preferable, and an alkylene group is particularly preferable. The spacer group is preferably chain-like and may contain oxygen atoms or sulfur atoms that are not adjacent to each other. The spacer group may have a substituent and may be substituted with a halogen atom (fluorine, chlorine, bromine), a cyano group, a methyl group, or an ethyl group.

Examples of the mesogenic group represented by M include all known mesogenic groups. In particular, a group represented by the following general formula (II) is preferable.
Formula (II): - (- W 1 -L 5) n-W 2 -
In the formula, W ¹ and W ² each independently represent a divalent cycloaliphatic group, a divalent aromatic group or a divalent heterocyclic group, L ⁵ represents a single bond or a linking group, and Specific examples of the group include specific examples of groups represented by L ^{1 to} L ⁴ in the formula (I), —CH ₂ —O—, and O—CH ₂ —. n represents 1, 2 or 3.

W ¹ and W ² include 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5diyl, 1,3,4-thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, pyridazine-3,6-diyl . In the case of 1,4-cyclohexanediyl, there are trans isomers and cis isomers, but either isomer may be used, and a mixture in any proportion may be used. More preferably, it is a trans form. W ¹ and W ² may each have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, etc.), and an alkoxy group having 1 to 10 carbon atoms. (Methoxy group, ethoxy group, etc.), C1-10 acyl group (formyl group, acetyl group, etc.), C1-10 alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), carbon atom Examples thereof include an acyloxy group having 1 to 10 (acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like.

  Preferred examples of the basic skeleton of the mesogenic group represented by the general formula (II) are shown below. These may be substituted with the above substituents.

  Examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto. The compound represented by the general formula (I) can be synthesized by the method described in JP-T-11-513019.

  The rod-like liquid crystal compound may be selected from liquid crystal compounds exhibiting a smectic A phase. Examples of such liquid crystal compounds are shown below, but are not limited to the following examples.

  As another aspect of the present invention, there is an aspect in which a discotic liquid crystal is used for the optically anisotropic layer. The optically anisotropic layer is preferably a layer of a low molecular weight liquid crystal discotic compound such as a monomer or a polymer layer obtained by polymerization (curing) of a polymerizable liquid crystal discotic compound. Examples of the discotic (discotic) compound include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physicslett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, page 2655 (1994), and azacrown-based and phenylacetylene-based macrocycles. The above discotic (discotic) compounds generally have a discotic nucleus at the center of the molecule, and groups (L) such as linear alkyl groups, alkoxy groups, and substituted benzoyloxy groups are substituted in a radial pattern. In other words, it has liquid crystallinity and generally includes a so-called discotic liquid crystal. However, when such an aggregate of molecules is uniformly oriented, it exhibits negative uniaxiality, but is not limited to this description. Further, in the present invention, it is not necessary that the final product is formed from a discotic compound, for example, the low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by a reaction such as heat or light to have a high molecular weight and lose liquid crystallinity.

In the present invention, it is preferable to use a discotic liquid crystalline compound represented by the following general formula (III).
Formula (III): D (-LP) n
In the formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12.

  In the formula (III), preferred specific examples of the discotic core (D), the divalent linking group (L) and the polymerizable group (P) are (D1) described in JP-A No. 2001-4837, respectively. To (D15), (L1) to (L25), (P1) to (P18), and the disk-shaped core (D), divalent linking group (L) and polymerizable group ( The contents regarding P) can be preferably applied here.

  Preferred examples of the discotic compound are shown below.

  The optically anisotropic layer is formed by applying a fluid containing a liquid crystal compound (for example, a solution of a liquid crystal compound) in an area separated by a black matrix by an ink jet method to obtain an alignment state exhibiting a desired liquid crystal phase. Thereafter, the layer is preferably a layer prepared by fixing the alignment state by irradiation with heat or ionizing radiation. It is preferable that the optically anisotropic layer exhibits biaxiality because various liquid crystal cells, particularly VA mode liquid crystal cells can be accurately compensated for viewing angle. As the liquid crystal composition exhibiting biaxiality, a liquid crystal composition described in JP-A-2005-338744 is preferable. Further, when a rod-like liquid crystal compound having a reactive group is used as the liquid crystal compound, in order to develop biaxiality, a cholesteric alignment or a hybrid cholesteric alignment twisted while gradually changing the tilt angle in the thickness direction, It needs to be distorted by polarized light irradiation. As a method for distorting the alignment by irradiation with polarized light, a method using a dichroic liquid crystalline polymerization initiator (EP1389199 A1) or a method using a rod-like liquid crystalline compound having a photoalignable functional group such as a cinnamoyl group in the molecule (special feature). No. 2002-6138). Any of them can be used in the present invention.

  When a rod-like liquid crystal compound having a reactive group and a discotic liquid crystal compound are used as the liquid crystal compound, the liquid crystal compound may be fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, hybrid alignment, and twist alignment. Good. Horizontal alignment means that the disk surface of the core of the discotic liquid crystalline compound is parallel to the horizontal plane of the support, but is not strictly required to be parallel. In this specification, the horizontal plane is defined as the horizontal plane. It shall mean an orientation with an inclination angle of less than 10 degrees.

  In the case of laminating two or more optically anisotropic layers made of a liquid crystalline compound, the combination of liquid crystalline compounds is not particularly limited, and a laminate of layers made of all discotic liquid crystalline compounds, all made of rod-like liquid crystalline compounds. It may be a laminate of layers composed of a layer, a layer composed of a discotic liquid crystalline compound and a layer composed of a rod-shaped liquid crystalline compound. The combination of the alignment states of the layers is not particularly limited, and optically anisotropic layers having the same alignment state may be stacked, or optically anisotropic layers having different alignment states may be stacked.

[A-plate and C-plate]
A uniaxial birefringent layer whose refractive index in the thickness direction is larger than the in-plane refractive index is called a positive C plate. The positive C plate can be realized by vertical alignment of polymerizable liquid crystal.
A uniaxial birefringent layer having an optical axis in the plane and having a refractive index of the slow axis larger than the refractive index in the thickness direction is referred to as a positive A plate. The positive A plate can be realized by horizontal alignment of rod-like liquid crystals.
A positive A-plate may be used as a second optically anisotropic layer to be described later. When a positive A-plate is used as the second optically anisotropic layer, Δn of the rod-like liquid crystal exhibiting the nematic phase and / or smectic A phase used for the production thereof preferably exhibits reverse dispersion in the visible light region. That is, it is preferable to satisfy the following formulas (I) and (II), and it is more preferable to satisfy the following formulas (I) -1 and (II) -1.
(I): Δn (450 nm) / Δn (550 nm) <1
(II): Δn (650 nm) / Δn (550 nm)> 1
(I) -1: 0.60 <Δn (450 nm) / Δn (550 nm) <0.99
(II) -1: 1.01 <Δn (650 nm) / Δn (550 nm) <1.35
When a liquid crystal material having a reverse dispersion of Δn is used, the first optical anisotropic layer that is a positive A-plate and a positive C-plate with reverse dispersion can be manufactured without adjusting the film thickness and the like. . However, by adjusting the film thickness, for example, a positive A-plate of Re (R layer)> Re (G layer)> Re (B layer) can be obtained. [Delta] n may be inversely dispersible in visible light, i.e., not satisfying the above formulas (I) and (II). Re (R layer), Re (G layer), and Re (B layer) are above or below the R, G, and B regions of the color filter layer when the color filter layer is an RGB, RGBW color filter, or the like. It means the in-plane retardation of each region of the first optically anisotropic layer arranged.

  Examples of the rod-like liquid crystal satisfying the formulas (I) and (II) include the rod-like liquid crystal represented by the general formula (1) or (2) described in Japanese Patent Application No. 2006-339233, more specifically. Includes the following liquid crystal compounds.

A uniaxial birefringent layer having an optical axis in the thickness direction of the layer and having a refractive index in the thickness direction smaller than the in-plane refractive index is referred to as a negative C plate. The negative C plate can be realized by horizontal alignment of discotic liquid crystal or cholesteric alignment of rod-like liquid crystal.
A uniaxial birefringent layer having an optical axis in the plane and having a refractive index of the slow axis equal to the refractive index in the thickness direction is referred to as a negative A plate. The negative A plate can be realized by the vertical alignment of the discotic liquid crystal.

  The first optically anisotropic layer is preferably formed by applying a coating liquid containing a liquid crystalline compound and the following polymerization initiator and other additives by an inkjet method. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Fixation of alignment state of liquid crystalline composition]
The aligned liquid crystalline composition is fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystalline composition. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by weight, more preferably 0.5 to 5% by weight, based on the solid content of the coating solution. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under a nitrogen atmosphere or under heating conditions.

  The first optically anisotropic layer may be a layer in which in-plane retardation is generated by photo-alignment by polarized light irradiation. This polarized light irradiation may be performed at the same time as the photopolymerization process in the above-described orientation fixing, or may be further fixed by non-polarized light irradiation after first polarized light irradiation, or fixed first by non-polarized light irradiation. Then, photo-alignment may be performed by irradiation with polarized light. Note that an optically anisotropic layer exhibiting in-plane retardation generated by photo-alignment by polarized light irradiation is particularly excellent for compensating the viewing angle of a VA mode liquid crystal display device.

[Optical alignment by polarized irradiation]
The first optically anisotropic layer may be a layer that exhibits in-plane retardation due to photo-alignment by irradiation with polarized light. In order to obtain a large in-plane retardation, polarized light irradiation needs to be performed first after coating and alignment of the liquid crystal compound layer. The polarized light irradiation is preferably performed in an inert gas atmosphere having an oxygen concentration of 0.5% or less. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. Although there is no restriction | limiting in particular about the kind of liquid crystalline compound hardened | cured by polarized light irradiation, The liquid crystalline compound which has an ethylenically unsaturated group as a reactive group is preferable. The irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably has a peak at 350 to 400 nm.

[Post-curing by UV irradiation after polarized irradiation]
The first optical anisotropic layer increases the reaction rate of the reactive group (post-curing) by further irradiating polarized or non-polarized ultraviolet rays after the first polarized irradiation (irradiation for photo-alignment), In addition to improving adhesion and the like, it becomes possible to produce at a high conveyance speed. The post-curing of the present invention may be polarized or non-polarized, but is preferably polarized. Moreover, it is preferable to carry out post-curing twice or more, and polarized light or non-polarized light may be combined with polarized light and non-polarized light. However, when combined, it is preferable to irradiate polarized light before non-polarized light. Irradiation with ultraviolet rays may or may not be replaced with an inert gas, but is preferably performed in an inert gas atmosphere having an oxygen concentration of 0.5% or less. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. In the case of polarized light irradiation, the irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably 350 to 400 nm. In the case of non-polarized light irradiation, it preferably has a peak at 200 to 450 nm, and more preferably has a peak at 250 to 400 nm.

  The optical characteristics of the first optically anisotropic layer are preferably adjusted to optical characteristics that are optimal for viewing angle compensation when R light, G light, and B light are incident. That is, when the color filter layer is colored red and used for forming the R layer of the color filter, the optical characteristics of the optical anisotropic layer are optimally adjusted for viewing angle compensation when R light is incident, When colored green, the optical properties of the optically anisotropic layer are optimally adjusted for viewing angle compensation when G light is incident, and when colored blue, the optical properties of the optically anisotropic layer Is preferably optimally adjusted for viewing angle compensation when B light is incident. The optical characteristics of the optically anisotropic layer are preferably in a preferable range depending on, for example, the type of liquid crystal compound, the type or addition amount of the alignment control agent, the type of alignment film, the rubbing treatment conditions of the alignment film, the film thickness, or the polarization irradiation conditions. Can be adjusted.

[Horizontal alignment control agent]
By containing at least one compound represented by the following general formulas (1) to (3) in the composition for forming the optically anisotropic layer, the molecules of the liquid crystalline compound are substantially horizontally aligned. be able to. In the present invention, “horizontal alignment” means that in the case of a rod-like liquid crystal, the molecular long axis is parallel to the horizontal plane of the transparent support. In the case of a disc-like liquid crystal, the disc surface of the core of the disc-like liquid crystal compound. And the horizontal plane of the transparent support is parallel, but it is not required to be strictly parallel, and in this specification, an inclination angle with the horizontal plane is less than 10 degrees. To do. The inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.
Hereinafter, the following general formulas (1) to (3) will be described in order.

General formula (1)

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ^{3 each} represent a single bond or a divalent linking group. The substituent represented by each of R ^{1 to} R ³ is preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), an aryl group (particularly a fluorine-substituted alkyl). An aryl group having a group is preferred), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. The divalent linking groups represented by X ¹ , X ² and X ³ are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NR ^a — ( R ^a is ^a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO ₂ — and combinations thereof. Preferably there is. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NR ^a —, —O—, —S—, and —SO ₂ —. It is more preferable that the divalent linking group is a combination of at least two groups. The alkylene group preferably has 1 to 12 carbon atoms. The alkenylene group preferably has 2 to 12 carbon atoms. The number of carbon atoms of the divalent aromatic group is preferably 6-10.

General formula (2)

In the formula, R represents a substituent, and m represents an integer of 0 to 5. When m represents an integer greater than or equal to 2, several R may be same or different. Preferred substituents for R are the same as those recited as preferred ranges for the substituents represented by R ¹ , R ² , and R ³ . m preferably represents an integer of 1 to 3, particularly preferably 2 or 3.

General formula (3)

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each preferably a substituent represented by R ¹ , R ² and R ³ in the general formula (I). It is listed as a thing. As the horizontal alignment agent used in the present invention, compounds described in Japanese Patent Application No. 2003-331269 can be used, and the synthesis method of these compounds is also described in the specification.

  The amount of the compound represented by any one of the general formulas (1) to (3) is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the mass of the liquid crystal compound. 0.02 to 1% by mass is particularly preferable. In addition, the compounds represented by the general formulas (1) to (3) may be used alone or in combination of two or more.

[Vertical alignment control agent]
The composition for forming the optically anisotropic layer contains at least one additive for controlling the alignment state of the liquid crystalline compound at the air interface and the alignment film interface in a substantially vertical manner, thereby allowing the molecules of the liquid crystalline compound to be contained. A substantially vertical alignment can be achieved. As the vertical alignment control agent for the rod-like liquid crystal, the compound described in JP-A-2006-106662 can be used, and for the vertical alignment control of the disk-like liquid crystal, the method described in JP-A-2005-222004, JP-A-2005. The method described in JP-A-196015, the method described in JP-A-2005-196016, the method described in JP-A-2006-85098, the method described in JP-A-2006-106662, and the method described in JP-A-2006-113500 The method can be used. In the present invention, “vertical alignment” means that in the case of a rod-like liquid crystal, the molecular long axis and the horizontal plane of the transparent support are perpendicular to each other. In the case of a disc-like liquid crystal, the disc surface of the core of the disc-like liquid crystal compound. The horizontal plane of the transparent support is vertical, but it is not required to be strictly vertical. In the present specification, an inclination angle between the horizontal plane and 70 to 90 degrees is meant. And The inclination angle is preferably 75 to 90 degrees, and most preferably 80 to 90 degrees.
[Alignment layer]
As described above, an alignment layer may be used to form the optically anisotropic layer. The alignment layer is generally provided on a transparent support or a color filter layer coated on the transparent support. The alignment layer functions so as to define the alignment direction of the liquid crystal compound provided thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer. Preferred examples of the alignment layer include a layer subjected to a rubbing treatment of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, and ω-tricosanoic acid, dioctadecylmethylammonium chloride and stearyl Examples thereof include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field.

  Examples of organic compounds for the alignment layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol, poly (N-methylolacrylamide), styrene / vinyltoluene copolymer. , Polymers such as chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethyl cellulose, polyethylene, polypropylene and polycarbonate, and Examples of the compound include a silane coupling agent. Examples of preferred polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol, and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).

  A polymer is preferably used for forming the alignment layer. The type of polymer that can be used can be determined according to the orientation (particularly the average tilt angle) of the liquid crystal compound. For example, in order to align the liquid crystalline compound horizontally, a polymer that does not decrease the surface energy of the alignment layer (ordinary alignment polymer) is used. Specific types of polymers are described in various documents about liquid crystal cells or optical compensation sheets. For example, polyvinyl alcohol or modified polyvinyl alcohol, a copolymer with polyacrylic acid or polyacrylate, polyvinyl pyrrolidone, cellulose, or modified cellulose are preferably used. The alignment layer material may have a functional group capable of reacting with the reactive group of the liquid crystal compound. The reactive group can be introduced by introducing a repeating unit having a reactive group in the side chain or as a substituent of a cyclic group. It is more preferable to use an alignment layer that forms a chemical bond with the liquid crystal compound at the interface. Such an alignment layer is described in JP-A-9-152509, and acid chloride or Karenz MOI (manufactured by Showa Denko KK). The modified polyvinyl alcohol in which an acrylic group is introduced into the side chain by using The thickness of the alignment layer is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

  A polyimide film (preferably fluorine atom-containing polyimide) widely used as an alignment layer for LCD is also preferable as the organic alignment layer. For this, polyamic acid (for example, LQ / LX series manufactured by Hitachi Chemical Co., Ltd., SE series manufactured by Nissan Chemical Co., Ltd., etc.) was applied to the support surface and baked at 100 to 300 ° C. for 0.5 to 1 hour. Thereafter, it is obtained by rubbing.

  Moreover, the rubbing process can utilize a processing method widely adopted as a liquid crystal alignment process of LCD. That is, a method of obtaining the orientation by rubbing the surface of the orientation layer in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. In general, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are flocked on average.

Further, as a vapor deposition material for the inorganic oblique vapor deposition film, SiO is a representative, and metal oxides such as TiO ₂ and ZnO ₂ , fluorides such as MgF 2, and metals such as Au and Al can be cited. The metal oxide can be used as an oblique deposition material as long as it has a high dielectric constant, and is not limited to the above. The inorganic oblique deposition film can be formed using a deposition apparatus. An inorganic oblique vapor deposition film can be formed by fixing the film (support) and performing vapor deposition, or moving the long film and performing continuous vapor deposition.

When the optically anisotropic layer is formed by fixing a substantially vertically aligned rod-like liquid crystal, the optically anisotropic layer can be obtained by using a compound described in JP-A-2006-106662 as a vertical alignment control agent. Can be formed directly on the glass substrate without an alignment layer.
[Color filter layer]
In the present invention, the color filter layer of the substrate may be formed from a colored resin composition. The colored resin composition preferably contains at least (1) a monomer or oligomer and (2) a colorant such as a dye or pigment. Moreover, when making it harden | cure by light etc., you may contain a (3) photoinitiator further. Furthermore, in order to control film physical properties, (4) a binder may be included. Hereinafter, the components (1) to (4) will be described.

(1) Monomer or oligomer The radical polymerizable monomer or oligomer used in the color filter layer is a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Is preferred. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the colored resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred.

  Examples of the cationic polymerizable monomer or oligomer used in the color filter layer include cyclic ethers, cyclic formals, acetals, vinyl alkyl ethers, compounds containing thiirane groups, bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins. And epoxy compounds such as epoxidized unsaturated fatty acid and epoxidized polybutadiene. Examples of such monomers or oligomers include compounds described in Hiroaki Kakiuchi's “New Epoxy Resin” Shoshodo (published in 1985), “Epoxy Resin” edited by Kuniyuki Hashimoto, Nikkan Kogyo Shimbun (1969), etc. Other trifunctional glycidyl ethers (trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.), tetra- or higher functional glycidyl ethers (sorbitol tetraglycidyl ether, Pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc.) trifunctional or higher cycloaliphatic epoxy (Epolide GT-) 01, Epolide GT-401, EHPE (manufactured by Daicel Chemical Industries, Ltd.), phenol novolac resin polycyclohexyl epoxy methyl ether, etc., trifunctional or more oxetanes (OX-SQ, PNOX-1009 (above, Tojo) Synthetic Co., Ltd.) and the like.

  The monomer or oligomer used for the color filter layer may be contained in the optically anisotropic layer.

(2) Colorant Known colorants (dyes and pigments) can be added to the colored resin composition. In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the colored resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly preferably 0.08 μm or less. .
Examples of the known dyes or pigments include Victoria Pure Blue BO (C.I. 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 5, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185;

C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73; C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment Red. 8, C.I. I. Pigment red 9, C.I. I. Pigment Leck 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265;

C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment Blue 60
C. I. Pigment green 7, C.I. I. Pigment Green 36
C. I. Pigment brown 23, C.I. I. Pigment Brown 25
C. I. Pigment black 1, C.I. I. Pigment black 7 and the like.

  As the colorant in the present invention, among the above-mentioned colorants, (i) R (red) colored resin composition is C.I. I. Pigment Red 254 is C.I. in (ii) G (green) colored resin composition. I. In the colored resin composition of (iii) B (blue), CI Pigment Green 36 is C.I. I. Pigment Blue 15: 6 is a preferable example. Furthermore, the above pigments may be used in combination.

  In the present invention, the combination of the above-described pigments preferably used in combination is C.I. I. In pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment yellow 139 or C.I. I. A combination with Pigment Violet 23; I. In Pigment Green 36, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 138 or C.I. I. A combination with CI Pigment Yellow 180, and C.I. I. In Pigment Blue 15: 6, C.I. I. Pigment violet 23 or C.I. I. A combination with Pigment Blue 60 is mentioned.

  C. in the pigment when used together in this way. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. The content of Pigment Blue 15: 6 is C.I. I. Pigment Red 254 is preferably 80% by weight or more, particularly preferably 90% by weight or more. C. I. The pigment green 36 is preferably 50% by weight or more, particularly preferably 60% by weight or more. C. I. Pigment Blue 15: 6 is preferably 80% by weight or more, particularly preferably 90% by weight or more.

  The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

  The colorant (pigment) used in the present invention preferably has a number average particle diameter of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm. When the number average particle diameter of the pigment is less than 0.001 μm, the particle surface energy is increased and the particles are easily aggregated, so that it is difficult to disperse the pigment and it is difficult to keep the dispersion state stable. On the other hand, if the number average particle diameter of the pigment exceeds 0.1 μm, the polarization is canceled by the pigment, and the contrast is lowered. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, The average value of 100 is said.

  The contrast of the colored pixels can be improved by reducing the particle size of the dispersed pigment. Reduction of the particle size can be achieved by adjusting the dispersion time of the pigment dispersion. For dispersion, the known disperser described above can be used. The dispersion time is preferably 10 to 30 hours, more preferably 18 to 30 hours, and most preferably 24 to 30 hours. When the dispersion time is less than 10 hours, the pigment particle size is large, the polarization due to the pigment is canceled, and the contrast may be lowered. On the other hand, if it exceeds 30 hours, the viscosity of the dispersion liquid increases and application may be difficult. Further, in order to make the difference in contrast between two or more colored pixels within 600, the pigment particle diameter is adjusted to obtain a desired contrast.

  The contrast of each colored pixel of the color filter formed from the color filter layer is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast of each colored pixel constituting the color filter is 2000 or less, when an image of a liquid crystal display device having the color pixel is observed, an overall whitish impression is obtained, which is not preferable. Further, the difference in contrast between the colored pixels is preferably within 600, more preferably within 410, still more preferably within 350, and most preferably within 200. It is preferable that the contrast difference between the colored pixels is within 600 because the amount of light leakage from each colored pixel portion during black display is not significantly different, and the color balance of black display is good.

(3) Photopolymerization initiator As the photopolymerization initiator or photopolymerization initiator system used in the color filter layer, a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, a US patent No. 2,448,828, an acyloin ether compound described in U.S. Pat. No. 2,722,512 and an aromatic acyloin compound substituted with an α-hydrocarbon, U.S. Pat. No. 3,046,127 and U.S. Pat. No. 2,951,758. A polynuclear quinone compound described in the specification, a combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516 and a trihalomethyl-s -Triazine compounds, described in U.S. Pat. No. 4,239,850 Trihalomethyl - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example. The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

  Examples of cationic polymerization initiators include aryldiazonium salts of Lewis acids such as etrafluoroborate and hexafluorophosphenol, double salts such as diaryliodonium salts and triarylsulfonium luster, benzylsilyl ether, o-nitrobenzylsilyl ether, triphenyl ( Examples thereof include a mixed system of a silanol-generating silane compound such as (t-butyl) peroxysilane and an aluminum complex such as tris (ethylacetoacetate) aluminum. The content of the cationic polymerization initiator based on the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

  In the present invention, these photopolymerization initiators may be used in combination with two or more different photoreaction mechanisms.

(4) Binder As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. As disclosed in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Can be mentioned.
Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid, and other monomers can be used. Mention may be made of multi-component copolymers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer.
As content in the dark color composition of a binder, 20-50 mass% is preferable with respect to the total solid (mass) of a layer or a composition, and 24-45 mass% is more preferable.

  In the present specification, “contrast of colored pixels” means a contrast that is individually evaluated for each color of R, G, and B constituting the color filter. The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. Note that the polarizing plate used for the contrast measurement is the same as the polarizing plate used for the liquid crystal display device using the color filter.

  In the color filter formed of the color filter layer, an appropriate surfactant may be contained in the colored resin composition from the viewpoint of effectively preventing display unevenness (color unevenness due to film thickness variation). preferable. The surfactant can be used as long as it is mixed with the photosensitive resin composition of the present invention. Preferred surfactants used in the present invention include JP2003-337424A [0090] to [0091], JP2003-177522A [0092] to [0093], and JP2003-177523A [0094]. ] To [0095], JP 2003-177521 A [0096] to [0097], JP 2003-177519 A [0098] to [0099], JP 2003-177520 A [0100] to [0101]. [0102] to [0103] of JP-A-11-133600 and surfactants disclosed as inventions of JP-A-6-16684 are preferred. In order to obtain a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) ) Or two or more types are preferable, and a fluorine-based surfactant is most preferable. When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. If the number of fluorine atoms is too large, it is not preferable in that the solubility in an ordinary solvent not containing fluorine is lowered. When the number of fluorine atoms is too small, it is not preferable in that the effect of improving unevenness cannot be obtained.

  As a particularly preferred surfactant, a monomer represented by the following general formula (a) and general formula (b) is included, and the mass ratio of the general formula (a) / general formula (b) is 20/80 to 60 / The thing containing 40 copolymers is mentioned.

  In the formula, R1, R2 and R3 each independently represent a hydrogen atom or a methyl group, and R4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 18, and m represents an integer of 2 to 14. p and q represent integers of 0 to 18, but are not included when both p and q are simultaneously 0.

  A particularly preferred surfactant represented by the general formula (a) is referred to as a monomer (a), and a monomer represented by the general formula (b) is referred to as a monomer (b). CmF2m + 1 shown in the general formula (a) may be linear or branched. m shows the integer of 2-14, Preferably it is an integer of 4-12. The content of CmF2m + 1 is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, based on the monomer (a). R1 represents a hydrogen atom or a methyl group. Moreover, n shows 1-18, and 2-10 are preferable especially. R2 and R3 shown in the general formula (b) each independently represent a hydrogen atom or a methyl group, and R4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each represent an integer of 0 to 18, but p and q do not include 0. p and q are preferably 2 to 8.

  Moreover, as a particularly preferable monomer (a) contained in one molecule of the surfactant, those having the same structure or those having different structures within the above defined range may be used. The same applies to the monomer (b).

  The weight average molecular weight Mw of the particularly preferable surfactant is preferably 1000 to 40000, and more preferably 5000 to 20000. The surfactant for use in the present invention contains the monomers represented by the general formula (a) and the general formula (b), and the mass ratio of the general formula (a) / the general formula (b) is 20/80 to 60/40. It is characterized by containing the copolymer of these. Particularly preferred 100 parts by weight of the surfactant is preferably such that the monomer (a) is 20 to 60 parts by weight, the monomer (b) is 80 to 40 parts by weight, and other optional monomers are the remaining parts by weight. It is preferable that the monomer (a) is 25 to 60 parts by mass, the monomer (b) is 60 to 40 parts by mass, and the other optional monomers are the remaining parts by mass.

  Examples of the copolymerizable monomer other than the monomers (a) and (b) include styrene, vinyl toluene, α-methyl styrene, 2-methyl styrene, chlorostyrene, vinyl benzoic acid, sodium vinylbenzene sulfonate, and aminostyrene. Styrene and its derivatives, substituted products, dienes such as butadiene and isoprene, acrylonitrile, vinyl ethers, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, styrene sulfonic acid maleic anhydride, silica And vinyl monomers such as cinnamate, vinyl chloride and vinyl acetate.

  Particularly preferred surfactants are copolymers such as monomer (a) and monomer (b), but the monomer sequence is not particularly limited and may be random or regular, for example, block or graft. Further, particularly preferable surfactants can be used by mixing two or more of those having different molecular structures and / or monomer compositions.

  As content of the said surfactant, 0.01-10 mass% is preferable with respect to the layer total solid of a color filter layer, and 0.1-7 mass% is especially preferable. The surfactant of the present invention contains a predetermined amount of a surfactant having a specific structure, an ethylene oxide group, and a polypropylene oxide group, and includes the color filter layer by containing it in a specific range in the color filter layer. Display unevenness of the liquid crystal display device is improved. If it is less than 0.01% by mass relative to the total solid content, the display unevenness is not improved, and if it exceeds 10% by mass, the effect of improving the display unevenness does not appear much. When a color filter is prepared by incorporating the above particularly preferred surfactant into the color filter layer, it is preferable in that display unevenness is improved.

Moreover, the following commercially available surfactant can also be used as it is. Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants, or silicon-based surfactants. be able to. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant.
The composition of the present invention may contain a solvent. As the solvent, water, alcohols, ketones, etc., the solvents described in “New Edition Solvent Pocketbook (edited by Organic Synthetic Science Association, published by Ohm)” The weight in the composition is preferably 50% or less, more preferably 30% or less.

[Partition wall]
In the present invention, the substrate has partition walls that separate fine regions (for example, pixel regions). It is preferable that the partition walls have a light-shielding property because they can be used as a black matrix (hereinafter, a partition that also functions as a black matrix is referred to as a “light-shielding partition wall”), and the configuration and manufacturing method can be simplified. The light-shielding barrier rib may be produced using, for example, a dark photosensitive composition containing a colorant (hereinafter sometimes referred to as “dark color composition”). Here, the dark color composition is a composition having a high optical density, and the value thereof is 2.0 to 10.0. The optical density of the dark color composition is preferably 2.5 to 6.0, particularly preferably 3.0 to 5.0. Further, since this dark color composition is preferably cured by a photoinitiating system as described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the partition may not be as desired, and if it exceeds 10.0, polymerization cannot be started and it is difficult to produce the partition itself. As long as it has such properties, the colorant (dark color) in the composition may be an organic substance (various dyes such as dyes and pigments) or carbon in various forms. It may be.

(Coloring agent)
The colorant used in the dark color composition will be specifically described.
For the dark color composition, organic pigments, inorganic pigments, dyes and the like can be suitably used, and light-shielding agents such as metal oxide powders such as carbon black, titanium oxide, and iron oxide, metal sulfide powders, and metal powders. In addition, a mixture of pigments such as red, blue, and green can be used. Known colorants (dyes and pigments) can be used. Among the known colorants, when a pigment is used, it is preferably dispersed uniformly in the dark color composition.
From the viewpoint of shortening the development time, the ratio of the colorant in the solid content of the dark color composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, and 50 to 55. More preferably, it is mass%.

  Specific examples of the known dyes or pigments include the color materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. The pigment described in JP-A-2005-17521 and the colorants described in [0080] to [0088] can be suitably used.

In the present invention, among the colorants, a black colorant is preferable. Illustrative examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.
The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. The portion is a liquid that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, page 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.

  The colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 0.1 μm, more preferably 0.01 to 0.08 μm, from the viewpoint of dispersion stability. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

  The dark color composition contains at least a polymerizable compound and a photopolymerization initiator in addition to the colorant (dark color body). Further, if necessary, a known additive such as a plasticizer, a filler, a stabilizer, a polymerization inhibitor, a surfactant, a solvent, an adhesion promoter, and the like can be further contained. Furthermore, the dark color composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.

  As a method for curing the dark color composition, a photoinitiating system is used. The photopolymerization initiator used here generates an active species that initiates polymerization of a polyfunctional monomer, which will be described later, upon irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray (also referred to as exposure). It is a compound to be obtained, and can be appropriately selected from known photopolymerization initiators or photopolymerization initiation systems.

  For example, trihalomethyl group-containing compounds, acridine compounds, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds Compound, etc. can be mentioned.

  Specifically, a trihalomethyl group-substituted trihalomethyloxazole derivative or s-triazine derivative described in JP-A No. 2001-117230, a trihalomethyl-s-triazine compound described in US Pat. No. 4,239,850, A trihalomethyl group-containing compound such as the trihalomethyloxadiazole compound described in Japanese Patent No. 4221976;

9-phenylacridine, 9-pyridylacridine, 9-pyrazinylacridine, 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) ) Butane, 1,5-bis (9acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, Bis such as 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane Acridine compounds such as (9-acridinyl) alkanes;

6- (p-methoxyphenyl) -2,4-bis (trichloromethyl) -s-triazine, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis ( Triazine compounds such as trichloromethyl) -s-triazine; 9,10-dimethylbenzphenazine, Michler's ketone, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, benzyldimethyl ketal, thioxanthone / amine, 2,2 ′ -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

  Among the above, at least one selected from a trihalomethyl group-containing compound, an acridine compound, an acetophenone compound, a biimidazole compound, and a triazine compound is preferable, and in particular, selected from a trihalomethyl group-containing compound and an acridine compound. It is preferable to contain at least one kind. Trihalomethyl group-containing compounds and acridine compounds are also useful in that they are versatile and inexpensive.

  Particularly preferred as the trihalomethyl group-containing compound is 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and as the acridine compound, 9-phenylacridine is preferred. Further, 6- [p- (N, N-bis (ethoxycarbonylmethyl) amino) phenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -5 Trihalomethyl group-containing compounds such as trichloromethyl-1,3,4-oxadiazole, and Michler's ketone, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2'-biimidazole.

  The said photoinitiator may be used independently and may use 2 or more types together. The total amount of the photopolymerization initiator in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition. When the total amount is less than 0.1% by mass, the photocuring efficiency of the composition is low and exposure may take a long time. When it exceeds 20% by mass, an image pattern formed during development is formed. May be lost or the pattern surface may be rough.

  The photopolymerization initiator may be configured using a hydrogen donor in combination. The hydrogen donor is preferably a mercaptan compound or an amine compound as defined below from the viewpoint that sensitivity can be further improved. The “hydrogen donor” herein refers to a compound that can donate a hydrogen atom to a radical generated from the photopolymerization initiator by exposure.

  The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan-based hydrogen donor). The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, and more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , Referred to as “amine-based hydrogen donor”). These hydrogen donors may have a mercapto group and an amino group at the same time.

  Specific examples of the mercaptan hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2. , 5-dimethylaminopyridine, and the like. Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable. Specific examples of the amine-based hydrogen donor include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl. Examples include -4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like. Of these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

  The hydrogen donor can be used alone or in admixture of two or more, and the formed image is less likely to fall off from the permanent support during development, and can be improved in strength and sensitivity. It is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors.

  Specific examples of the combination of the mercaptan hydrogen donor and the amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Examples thereof include bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone. More preferred combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylaminobenzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole. / 4,4'-bis (diethylamino) benzophenone.

  When the mercaptan hydrogen donor and the amine hydrogen donor are combined, the mass ratio (M: A) of the mercaptan hydrogen donor (M) to the amine hydrogen donor (A) is usually 1: 1-1: 4 is preferable, and 1: 1-1: 3 is more preferable. The total amount of the hydrogen donor in the dark color composition is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content (mass) of the dark color composition.

  As the polyfunctional monomer (polymerizable compound) of the dark color composition, the following compounds can be used alone or in combination with other monomers. Specifically, t-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2- Ethyl-2-butyl-propanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyoxy Ethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4-dihydroxy Nzenji (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate, (meth) acrylamide, xylylenebis (meth) acrylamide, and the like.

  Moreover, reaction of a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate with a diisocyanate such as hexamethylene diisocyanate, toluene diisocyanate, and xylene diisocyanate. Things can also be used.

  Of these, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and tris (2-acryloyloxyethyl) isocyanurate are particularly preferable.

  As content in the dark composition of a polyfunctional monomer, 5-80 mass% is preferable with respect to the total solid (mass) of a dark color composition, and 10-70 mass% is especially preferable. When the content is less than 5% by mass, the resistance to an alkaline developer at the exposed portion of the composition may be inferior, and when it exceeds 80% by mass, the tackiness of a dark color composition increases. Therefore, the handleability may be inferior.

The dark color composition may contain at least one binder. As the binder, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-53836. As disclosed in JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. Can be mentioned.
Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned. Furthermore, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably.
As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid, and other monomers can be used. Mention may be made of multi-component copolymers. These binders having a polar group may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer.

  As content in the dark color composition of a binder, 20-50 mass% is preferable with respect to the total solid (mass) of a layer or a composition, and 24-45 mass% is more preferable.

  The dark color composition may contain an organic solvent in addition to the components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

The dark color composition further includes the following components, such as surfactants, ultraviolet absorbers, and known additives such as plasticizers, fillers, stabilizers, thermal polymerization inhibitors, solvents, adhesion promoters, and the like. Can be contained. Furthermore, the photosensitive resin composition is preferably softened or tacky at a temperature of at least 150 ° C., and is preferably thermoplastic. From such a viewpoint, it can be modified by adding a compatible plasticizer.
<Surfactant>
When applying a dark color composition on a board | substrate, it can control to a uniform film thickness by containing surfactant in a dark color composition, and can prevent a coating nonuniformity effectively. Preferred examples of the surfactant include surfactants described in JP-A Nos. 2003-337424 and 11-133600. In addition, as content in the deep color composition of surfactant, 0.001-1% is common with respect to the total solid (mass) of this composition, 0.01-0.5 % Is preferable, and 0.03 to 0.3% is particularly preferable.
<Ultraviolet absorber>
The dark color composition may contain an ultraviolet absorber as necessary.
Examples of the ultraviolet absorber include compounds described in JP-A-5-72724, and compounds such as salicylates, benzophenones, benzotriazoles, cyanoacrylates, nickel chelates, and hindered amines.
For example, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy -3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel dibutyl Dithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -sebacate 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperenyl) Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine-2 -Yl] amino} -3-phenylcoumarin and the like.
In the case of using the ultraviolet absorber, the content of the ultraviolet absorber with respect to the total solid content of the dark color composition is generally 0.5 to 15%, preferably 1 to 12%, preferably 1.2 to 10%. Is particularly preferred.
<Thermal polymerization inhibitor>
The dark composition preferably contains a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.
When the thermal polymerization inhibitor is used, the content with respect to the total solid content of the dark color composition is generally 0.01 to 1%, preferably 0.02 to 0.7%, preferably 0.05 to 0%. .5% is particularly preferred.
Further, in addition to the above components, the dark color composition may contain “adhesion aid” described in JP-A-11-133600, other additives, and the like.

The light-shielding partition is preferably formed from the dark color composition. The light-shielding partition separates two or more pixel groups and is generally black, but is not limited to black. The light-shielding partition walls are preferably formed by exposing the dark color photosynthesis composition in an oxygen-poor atmosphere and then developing it.
Under an oxygen-poor atmosphere when photocuring such a dark-colored composition means an inert gas, a reduced pressure, or a protective layer that can block oxygen, and these are described in detail below. .
The inert gas refers to a general gas such as N ₂ , H ₂ , CO ₂ , or a rare gas such as He, Ne, Ar. Among these, N ₂ is preferably used because of safety, availability, and cost.

Under reduced pressure refers to a state of 500 hPa or less, preferably 100 hPa or less.
Examples of the protective layer capable of blocking oxygen include, for example, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose described in JP-A Nos. 46-2121 and 56-40824. Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches And a group of water-soluble salts thereof, styrene / maleic acid copolymers, maleate resins, and combinations of two or more thereof. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinyl pyrrolidone is preferably 1 to 75% by mass, more preferably 1 to 50% by mass, and still more preferably the alkali-soluble resin layer solid content. It is 10-40 mass%.
The oxygen permeability coefficient of the protective layer capable of blocking oxygen thus prepared is preferably 75 cm ³ / m ² · day · 1000 hPa or less, more preferably 50 cm ³ / m ² · day · 1000 hPa or less, and 25 cm ³ / m. ² · day · 1000 hPa or less is most preferable. When the oxygen permeability coefficient is more than 75 cm ³ / m ² · day · 1000 hPa, oxygen cannot be effectively blocked, and it becomes difficult to form the light-shielding partition walls in a desired shape.

  From the viewpoint of preventing color mixing, the height of the light-shielding partition walls is preferably 1 to 20 μm, more preferably 1.5 to 10 μm, and further preferably 2 to 5 μm.

(Photosensitive transfer material for barrier rib formation)
In order to realize such a light-shielding partition wall easily and at low cost, a photosensitive transfer material having at least a layer made of a photosensitive dark color composition and an oxygen blocking layer in this order on a temporary support is used. There is a technique to do. When such a material is used, since the layer made of the photosensitive dark color composition is protected by the oxygen blocking layer, it automatically becomes in an oxygen-poor atmosphere. Therefore, there is no need to carry out the exposure process under an inert gas or under reduced pressure, so that there is an advantage that the current process can be used as it is.
The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is alkali-soluble and includes at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, it is possible to exhibit good adhesion to a permanent support in a method for forming a light-shielding partition which will be described later.

  Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.

  For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.

  In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.

  Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl, and diphenyl phosphate.

  The temporary support in the above photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers.

(Formation of light-shielding barriers using transfer materials)
Hereinafter, the case where a light-shielding partition is formed using a photosensitive transfer material will be described. A photosensitive transfer material having a photosensitive dark color composition layer, an oxygen barrier layer, and a cover sheet provided on the oxygen barrier layer is prepared on a temporary support. First, after removing and removing the cover sheet, the exposed surface of the oxygen barrier layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to increase productivity.

  Subsequently, it peels between a temporary support body and the photosensitive resin layer, and a temporary support body is removed. Subsequently, a desired photomask is disposed above the removal surface after removal of the temporary support, irradiated with ultraviolet rays from a light source, and developed using a predetermined processing solution after irradiation. As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water. Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

  Suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate). , Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Examples include morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin layer, methods such as rubbing with a rotating brush or wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the light-shielding partition wall shape suitable. It is also possible to put a water washing step after the development processing. In this development process, the light-shielding partition wall shape is formed as described above.

  Next, the color filter ink or the optical anisotropy forming fluid for forming each pixel such as RGB is made to enter the gap in the gap of the light-shielding partition formed in the development step. Before forming, the shape of the light-shielding partition may be fixed, and the means is not particularly limited, and examples thereof include the following. That is, 1) re-exposure after development (sometimes referred to as post-exposure), and 2) heat treatment at a relatively low temperature after development. The heat treatment here refers to heating a substrate having a light-shielding partition wall in an electric furnace, a drier or the like, or irradiating an infrared lamp.

Here, the exposure amount when performing the above 1) is 500 to 3000 mJ / cm ² , preferably 1000 to 2000 mJ / cm ² in the atmosphere, and lower exposure in the poor oxygen atmosphere. It is also possible to expose in quantity. Similarly, the heating temperature in the case of 2) is 50 to 120 ° C., preferably about 70 to 100 ° C., and the heating time is about 10 to 40 minutes. When the temperature is lower than 50 ° C., there is a concern that the light-shielding partition wall may not be cured, and when it is higher than 120 ° C., the shape of the light-shielding partition wall may be destroyed.

[Second optically anisotropic layer]
The liquid crystal display device of the present invention may further have an unpatterned second optically anisotropic layer inside or outside the cell. For the second optically anisotropic layer, for example, various wavelength plates and liquid crystal layers for the purpose of coloration due to birefringence and compensation of viewing angle, etc. can be used, and an appropriate optical according to the purpose of use can be used. Two or more optically anisotropic films having anisotropy can be laminated to control optical characteristics such as retardation. As such an optically anisotropic film, a film made of an appropriate polymer such as polycarbonate, norbornene resin, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene, other polyolefins, polyarylate, or polyamide is stretched. Examples thereof include an alignment film made of a liquid crystal compound such as a birefringent film or a liquid crystal polymer, and an alignment layer of a liquid crystal material supported by the film. In addition, a biaxially stretched film, a birefringent film stretched in two orthogonal directions, a bi-directionally stretched film such as a tilted oriented film, and the like are used. Examples of the inclined alignment film include a film obtained by bonding a heat shrink film to a polymer film and stretching or / and shrinking the polymer film under the action of the contraction force by heating, or a film obtained by obliquely aligning a liquid crystal polymer. Can be mentioned.

  In particular, as an optically anisotropic film capable of creating higher-performance optical characteristics by combining with the first optically anisotropic layer, a transparent optically anisotropic film described below and a cellulose acylate film having a small Re are described below. Preferably used.

<Transparent optical anisotropic film>
The second optically anisotropic layer is preferably a transparent optically anisotropic film having an in-plane retardation (Re) of 20 nm to 250 nm and a thickness direction retardation (Rth) of 10 nm to 350 nm. Such a film is preferably a film containing cellulose acylate and cycloolefin.
In order to effectively reduce the light leakage in the oblique direction of the polarizing plate, Re is more preferably 20 nm to 250 nm, and further preferably 20 nm to 200 nm. In order to effectively reduce light leakage in an oblique direction, Rth is more preferably 10 nm to 300 nm, and further preferably 20 nm to 250 nm. Within this range, the transparent optically anisotropic film may be optically uniaxial or biaxial.

  When a positive A-plate film is used as the second optically anisotropic layer, it is suitable for improving the contrast of the liquid crystal display device for IPS, and Re (550 nm) is 40 to 250 nm as the positive A-plate film. Yes, it is preferably 70 to 230 nm, and more preferably 100 to 180 nm. The wavelength dispersion is Re (450 nm) / Re (550 nm) = 0.6 to 1, preferably 0.65 to 0.95, and more preferably 0.7 to 0.9. Re (650 nm) / Re (550 nm) = 1 to 1.3, preferably 1.01 to 1.25, and more preferably 1.02 to 1.23.

<< Cellulose acylate film with small Re and Rth >>
As a cellulose acylate film having a small optical anisotropy (Re, Rth), the in-plane retardation Re at a wavelength of 630 nm is 10 nm or less (0 ≦ Re (630) ≦ 10), and the retardation Rth in the film thickness direction. Is preferably from -100 nm to 25 nm. More preferably, 0 ≦ Re (630) ≦ 5 and −60 ≦ Rth (630) ≦ 20, and further preferably 0 ≦ Re (630) ≦ 2 and −40 ≦ Rth (630) ≦. 15.

Furthermore, a cellulose acylate film having a small wavelength dispersion is preferable, and | Re (400) −Re (700) | ≦ 10 and | Rth (400) −Rth (700) | ≦ 35 are more preferable. More preferably, | Re (400) −Re (700) | ≦ 5 and | Rth (400) −Rth (700) | ≦ 25, most preferably | Re (400) −Re (700). | ≦ 3 and | Rth (400) −Rth (700) | ≦ 15.
By combining the patterned first optically anisotropic layer and the unpatterned second optically anisotropic layer having such optical characteristics, the viewing angle of the polarizing plate is effectively reduced. An expanding member can be provided.
Further, when a cellulose acylate film having a small Re is used as a protective film for a polarizing plate, there is an effect that the thickness of the first optically anisotropic layer can be reduced.
Among the acyl substituents substituted on the hydroxyl group of cellulose described above, in the case of substantially consisting of at least two kinds of acetyl group, propionyl group and butanoyl group, the total substitution degree is 2.50 to 3.00 Further, it was found that the optical anisotropy of the cellulose acylate film can be reduced. The degree of acyl substitution is more preferably 2.60 to 3.00, still more preferably 2.65 to 3.00. These cellulose acylates of the present invention are described in detail on pages 7 to 12 of the raw material cotton and the synthesis method thereof published by the Japan Society of Invention and Innovation (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Invention and Innovation). Has been.

  The cellulose acylate can be used as a single or a mixture of two or more different cellulose acylates.

  The cellulose acylate film may be produced using a cellulose acylate solution. In the cellulose acylate solution, various additives according to the use in each preparation step (for example, compounds that reduce optical anisotropy, wavelength dispersion adjusting agents, ultraviolet inhibitors, plasticizers, deterioration inhibitors, fine particles, optical Characteristic modifiers, etc.) can be added. Further, the addition may be performed at any time in the dope preparation step, but may be performed by adding a preparation step by adding an additive to the final preparation step of the dope preparation step.

The cellulose acylate film that can be used in the present invention preferably contains a compound that lowers Rth such that Rth in the film thickness direction satisfies the following formulas (3) and (4).
_{(3) (Rth (A)} -Rth (0)) /A≦-1.0
(4) 0.01 ≦ A ≦ 30
(In the formulas (3) and (4), Rth _(A) represents Rth (nm) of a film containing A% of a compound that lowers Rth, and Rth ₍₀₎ is the film, and Rth is R represents the Rth (nm) of the film not containing the compound for reducing, and A represents the weight (%) of the compound for reducing Rth when the weight of the film raw material polymer is 100.
The above formulas (3) and (4) are expressed as (3-I) (Rth _(A) −Rth ₍₀₎ ) /A≦−2.0.
(4-I) 0.1 ≦ A ≦ 20
More preferably.
As the compound for reducing the optical anisotropy of the cellulose acylate film, those described in JP-A-2006-30937 can be used.

  A biaxial polymer film may be used as the second optically anisotropic layer. In order to effectively reduce light leakage in an oblique direction, the polymer film preferably has a retardation Re (λ) of 20 nm to 150 nm, more preferably 40 nm to 115 nm, and 60 nm to 95 nm. More preferably. Further, in order to effectively reduce the light leakage in the oblique direction, Nz = (nx−nz) / by using the in-plane refractive indexes nx and ny (nx> ny) and the refractive index nz in the thickness direction. Nz defined by (nx-ny) is preferably 1.5 to 7, more preferably 2.0 to 5.5, and even more preferably 2.5 to 4.5.

  As long as the second optically anisotropic layer region has the optical characteristics, the material and form thereof are basically not particularly limited. For example, a retardation film made of a birefringent polymer film, a film obtained by applying a high molecular compound on a transparent support and then heated and salted, and a low molecular weight or high molecular liquid crystalline compound applied or transferred onto the transparent support Any of the retardation films having the retardation layer formed can be used. Moreover, each can also be laminated | stacked and used.

  The birefringent polymer film is preferably a film having excellent controllability of birefringence characteristics, transparency and heat resistance. In this case, the polymer material to be used is not particularly limited as long as it is a polymer capable of achieving uniform biaxial orientation, but is preferably a conventionally known material that can be formed by a solution casting method or an extrusion method, and is preferably a norbornene-based material. Polymers, polycarbonate polymers, polyarylate polymers, polyester polymers, aromatic polymers such as polysulfone, cellulose acylate, or polymers in which two or more of these polymers are mixed It is done.

The biaxial orientation of the film is a film made of the thermoplastic resin produced by an appropriate method such as an extrusion molding method or a casting film forming method, for example, a longitudinal stretching method using a roll, a lateral stretching method using a tenter, or a biaxial stretching method. It can be obtained by stretching. In the longitudinal stretching method using the roll, an appropriate heating method such as a method using a heating roll, a method of heating an atmosphere, or a method of using them together can be employed. In the biaxial stretching method using a tenter, an appropriate method such as a simultaneous biaxial stretching method using an all tenter method or a sequential biaxial stretching method using a roll tenter method can be employed.
Moreover, a thing with little orientation nonuniformity and phase difference nonuniformity is preferable. The thickness can be appropriately determined depending on the phase difference or the like, but is generally 1 to 300 μm, especially 10 to 200 μm, especially 20 to 150 μm from the viewpoint of thinning.

  As the norbornene-based polymer, norbornene and its derivatives, tetracyclododecene and its derivatives, dicyclopentadiene and its derivatives, methanotetrahydrofluorene and its monomers as a main component of a monomer polymer, Ring-opening polymer of norbornene monomer, ring-opening copolymer of norbornene monomer and other monomer capable of ring-opening copolymerization, addition polymer of norbornene monomer, copolymerizable with norbornene monomer Examples include addition copolymers with other monomers and hydrogenated products thereof. Among these, from the viewpoints of heat resistance, mechanical strength, and the like, a ring-opening polymer hydride of a norbornene monomer is most preferable. The molecular weight of the norbornene-based polymer, the polymer of the monocyclic olefin or the polymer of the cyclic conjugated diene is appropriately selected according to the purpose of use, but the cyclohexane solution (toluene solution if the polymer resin does not dissolve) The polyisoprene or polystyrene-converted weight average molecular weight measured by gel permeation chromatography is usually 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000. When the thickness is in the range, the mechanical strength of the film (A) and the moldability are highly balanced, which is preferable. Typical polymers include those described in JP2003-327800A and JP2004233604A.

  The acyl group of cellulose acylate may be an aliphatic group or an aromatic group. Examples include alkylcarbonyl, alkenylcarbonyl, aromatic carbonyl, aromatic alkylcarbonyl and the like. They may further have a substituted group. An ester group having a total carbon number of 22 or less is preferred. Preferred examples thereof include alkylcarbonyl groups having a total carbon number of 22 or less (for example, acetyl, propionyl, butyroyl, barrel, heptanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, hexadecanoyl, octadecanoyl, etc.), arylcarbonyl groups (Benzoyl, naphthaloyl, etc.), allylcarbonyl groups (acrylic, methacrylic, etc.), cinnamoyl groups are included. Among these, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate stearate, cellulose acetate benzoate, etc. are not particularly limited in the case of mixed esters, but preferably acetate is the total ester. It is preferable that it is 30 mol% or more.

  Among these, cellulose acylate is preferable, a photographic grade is particularly preferable, and a commercially available product may be used. Manufacturers of photographic grade cellulose triacetate include Daicel Chemical Industries, Ltd. (for example, LT-20, 30, 40, 50, 70, 35, 55, 105, etc.), Eastman Chemical (for example, CAB-551). 0.01, CAB-551-0.02, CAB-500-5, CAB-381-0.5, CAB-381-02, CAB-381-20, CAB-321-0.2, CAP-504 0.2, CAP-482-20, CA-398-3, etc.), Coatles, Hoechst, etc., any of which can use photographic grade cellulose acylate. In addition, a plasticizer, a surfactant, a retardation modifier, a UV absorber, and the like can be mixed for the purpose of controlling the mechanical properties and optical properties of the film. Details of these additives are described in, for example, JP-A Nos. 2002-277632 and 2002-182215.

As a method for forming the transparent resin into a sheet or film, for example, either a hot melt molding method or a solution casting method can be used. The heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, etc. Among these methods, mechanical strength, surface In order to obtain a film excellent in accuracy and the like, the extrusion molding method, the inflation molding method, and the press molding method are preferable, and the extrusion molding method is most preferable. The molding conditions are appropriately selected depending on the purpose of use and the molding method. In the case of the heat-melt molding method, the cylinder temperature is preferably set in the range of preferably 100 to 400 ° C, more preferably 150 to 350 ° C. The thickness of the sheet or film is preferably 10 to 300 μm, more preferably 30 to 200 μm.
The sheet or film may be stretched. When the glass transition temperature of the transparent resin is Tg, the stretching of the sheet or film is preferably in a temperature range of Tg-30 ° C to Tg + 60 ° C, more preferably in a temperature range of Tg-10 ° C to Tg + 50 ° C. In at least one direction, the stretching ratio is preferably 1.01 to 2 times. The stretching direction may be at least one direction, but when the sheet is obtained by extrusion, the direction is preferably the mechanical flow direction (extrusion direction) of the resin. A free shrink uniaxial stretching method, a fixed width uniaxial stretching method, a biaxial stretching method, and the like are preferable. The optical characteristics can be controlled by controlling the draw ratio and the heating temperature.

[Liquid Crystal Display]
By using the patterned first optically anisotropic layer and the second optically anisotropic layer that is not patterned as desired, a liquid crystal display device having a wide viewing angle can be provided. . TN mode liquid crystal cell retardation plates (optical compensation sheets) are described in JP-A-6-214116, US Pat. Nos. 5,583,679, 5,646,703, and German Patent 3,911,620A1. A retardation plate (optical compensation sheet) for liquid crystal cells in IPS mode or FLC mode is described in JP-A-10-54982. Furthermore, a retardation plate (optical compensation sheet) for an OCB mode or HAN mode liquid crystal cell is described in US Pat. No. 5,805,253 and International Publication WO96 / 37804. Furthermore, a retardation plate (optical compensation sheet) for a liquid crystal cell in STN mode is described in JP-A-9-26572. A VA mode liquid crystal cell retardation plate (optical compensation sheet) is described in Japanese Patent No. 2866372.

  The present invention can be used for liquid crystal display devices in various display modes such as TN, IPS, FLC, OCB, STN, VA and HAN modes. Among them, it is suitable for VA and IPS mode liquid crystal display devices.

[VA mode]
The liquid crystal display device of the present invention may use a VA mode. In view of improving the viewing angle, the VA mode liquid crystal display device of the present invention is a layer manufactured by fixing the cholesteric orientation of the rod-like liquid crystal as the first optical anisotropic layer, and the wavelength dispersion of Δn is the above formula (I). And a method using a negative C-plate as a second optically anisotropic layer using a rod-shaped liquid crystal satisfying (II) and a liquid crystal having a forward dispersion of Δn in the visible light region. It is preferable to use a positive A-plate of Re (R layer)> Re (G layer)> Re (B layer) and a negative C-plate as the second optical anisotropic layer.

[IPS mode]
The liquid crystal display device of the present invention may use an IPS mode. In terms of improving the viewing angle, the IPS mode liquid crystal display device of the present invention has a positive C plate or a negative A-plate as the first optical anisotropic layer, and the second optical anisotropic layer. As a positive A-plate or biaxial film. The positive C-plate used as the first optically anisotropic layer is preferably produced by fixing the vertical alignment of the rod-like liquid crystal, and the wavelength dispersion of Δn is represented by the formulas (I) and (II). It may be manufactured using a rod-shaped liquid crystal satisfying the above, or may be manufactured using other rod-shaped liquid crystals. The negative A-plate used as the first optically anisotropic layer is preferably manufactured by fixing the vertical alignment of the discotic liquid crystal. The positive A-plate used as the second optically anisotropic layer is preferably a polymer film whose Re wavelength dispersion satisfies the following formulas (III) and (IV).
(III) Re (450 nm) / Re (550 nm) <1
(Iv) Re (650 nm) / Re (550 nm)> 1

The biaxial film used as the second optically anisotropic layer has an in-plane retardation (Re) which is not 0, and the normal axis of the optical compensation sheet with the in-plane slow axis as the tilt axis (rotation axis). The retardation value measured by making light of wavelength λ nm incident from a direction inclined + 40 ° with respect to the direction, and the normal axis direction of the optical compensation sheet with the in-plane slow axis as the tilt axis (rotation axis) − It is preferable that the retardation values measured by making light having a wavelength λ nm incident from a direction inclined by 40 ° are substantially equal.
The biaxial film used as the second optically anisotropic layer has a retardation Re (λ) at a wavelength λnm of 20 nm to 150 nm, and an in-plane refractive index nx and ny (nx> ny). And the value Nz of the second optically anisotropic layer region defined by Nz = (nx−nz) / (nx−ny) using the refractive index nz in the thickness direction is 1.5 to 7. Is preferred.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Example 1
(Production method of black photosensitive composition for barrier rib preparation)
The black photosensitive composition K1 is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 RPM for 10 minutes, Next, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-diethoxycarbonylmethylamino) -3 in the amounts shown in Table 1 '-Bromophenyl] -s-triazine and surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes. . In addition, the quantity of Table 1 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
・ Dispersant (Compound 1 below) 0.65%
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%
<DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%
<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

(Formation of light-shielding barrier)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the glass substrate coater (manufactured by FAS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle has the composition described in Table 1 above. A black photosensitive composition K1 was applied. Subsequently, a portion of the solvent was dried for 30 seconds with a VCD (vacuum drying device, manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a black photosensitive film having a thickness of 10 μm Layer K1 was obtained.

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the black photosensitive layer K1 The distance was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² in a nitrogen atmosphere.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the black photosensitive layer K1, and then a KOH-based developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji Film) (Electronic Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure washing nozzle to remove the residue, and post exposure was performed at an exposure amount of 2000 mJ / cm 2 in the atmosphere to obtain a black having an optical density of 3.9. A partition was obtained. A fine region separated by the black partition was formed on the surface of the glass substrate.

(Preparation of coating liquid AL-1 for alignment layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as an alignment layer coating liquid AL-1.
──────────────────────────────────――
Coating liquid composition for alignment layer (%)
──────────────────────────────────――
Polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.) 3.21
Polyvinylpyrrolidone (Luvitec K30, manufactured by BASF) 1.48
Distilled water 52.1
Methanol 43.21
──────────────────────────────────――

(Preparation of coating liquid LC-R1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as the coating liquid LC-R1 for the optically anisotropic layer.
LC-1-1 was obtained from Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002). LC-1-2 was synthesized by the method described in EP1388538A1, page21.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 28.62
Chiral agent (Paliocolor LC756, BASF Japan)
3.40
4,4′-Azoxydianisole 0.52
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.36
Methyl ethyl ketone 66.0
──────────────────────────────────――

(Preparation of coating liquid LC-G1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-G1 for an optically anisotropic layer.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 28.38
Chiral agent (Paliocolor LC756, BASF Japan)
3.34
4,4′-Azoxydianisole 0.27
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.34
Methyl ethyl ketone 66.57
──────────────────────────────────――

(Preparation of coating liquid LC-B1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-B1 for an optically anisotropic layer.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 28.72
Chiral agent (Paliocolor LC756, BASF Japan)
3.36
4,4′-Azoxydianisole 0.03
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.34
Methyl ethyl ketone 66.45
───────────────────────────────────────

Color Filter Composition Table 2 shows the composition of each RGB pixel composition.

The composition of the composition in Table 2 is as follows.
[R pigment dispersion-1 composition]
──────────────────────────────────――
R pigment dispersion-1 composition (%)
──────────────────────────────────――
C. I. Pigment Red 254 8.0
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone 0.8
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, (weight average molecular weight 37,000) 8.0
Propylene glycol monomethyl ether acetate 83.2
──────────────────────────────────――

[R pigment dispersion-2 composition]
──────────────────────────────────――
R pigment dispersion-2 composition (%)
──────────────────────────────────――
C. I. Pigment Red 177 18.0
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio,
(Weight average molecular weight 37,000) 12.0
Propylene glycol monomethyl ether acetate 70.0
──────────────────────────────────――

[G pigment dispersion composition]
──────────────────────────────────――
G pigment dispersion composition (%)
──────────────────────────────────――
C. I. Pigment Green 36 18.0
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio,
(Weight average molecular weight 37,000) 12.0
Cyclohexanone 35.0
Propylene glycol monomethyl ether acetate 35.0
──────────────────────────────────――

[Binder 1 composition]
──────────────────────────────────――
Binder 1 composition (%)
──────────────────────────────────――
Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio (weight average molecular weight 40,000) 27.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────――

[Binder 2 composition]
──────────────────────────────────――
Binder 2 composition (%)
──────────────────────────────────――
Benzyl methacrylate / methacrylic acid / methyl methacrylate =
Random copolymer with a 38/25/37 molar ratio (weight average molecular weight 30,000) 27.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────――

[Binder 3 composition]
──────────────────────────────────――
Binder 3 composition (%)
──────────────────────────────────――
Benzyl methacrylate / methacrylic acid / methyl methacrylate =
36/22/42 molar ratio random copolymer (weight average molecular weight 30,000) 27.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────――

[DPHA composition]
──────────────────────────────────――
DPHA solution composition (%)
──────────────────────────────────――
KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 76.0
Propylene glycol monomethyl ether acetate 24.0
──────────────────────────────────――

(Preparation of R layer forming solution PP-R1)
The R layer forming liquid PP-R1 is first weighed in the amounts of R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 2, and mixed at a temperature of 24 ° C. (± 2 ° C.). And then stirred for 10 minutes at 150 rpm, then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2 , 4-Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine were weighed and this was measured at a temperature of 24 ° C. (± 2 ° C.). Add in order and stir at 150 rpm for 10 minutes, then weigh out the amount of ED152 listed in Table 2, mix at a temperature of 24 ° C. (± 2 ° C.) and stir at 150 rpm for 20 minutes Further weighed amount of Megafac F-176PF according to Table 2, and stirred 30rpm30 minutes was added at a temperature 24 ° C. (± 2 ° C.), it was obtained by filtering with a nylon mesh # 200.

(Preparation of G-layer forming solution PP-G1)
The G-layer forming liquid PP-G1 was first weighed in the amounts of G pigment dispersion, CF yellow EX3393, and propylene glycol monomethyl ether acetate listed in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.) and 150 rpm for 10 minutes. Stirring and then the amounts of methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, 2,4- Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine are weighed out and added in this order at a temperature of 24 ° C. (± 2 ° C.). And stirred at 150 rpm for 30 minutes, and then weighed out the amount of Megafac F-176PF shown in Table 2 to a temperature of 24 ° C. (± 2 ) Was added with stirring 30rpm5 minutes, and filtering the mixture through a nylon mesh # 200.

(Preparation of B-layer forming solution PP-B1)
B-layer forming solution PP-B1 is first weighed in the amounts of CF Blue EX3357, CF Blue EX3383 and propylene glycol monomethyl ether acetate listed in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, and phenothiazine in the amounts shown in Table 2 were weighed, and the temperature was 25 At a temperature of 40 ° C. (± 2 ° C.) and stirred at 150 rpm for 30 minutes, and the amount of Megafac F-176PF shown in Table 2 was weighed out to a temperature of 24 ° C. (± 2 rpm) and stirred at 30 rpm for 5 minutes and filtered through nylon mesh # 200.

(Preparation of alignment layer)
The alignment layer coating liquid AL-1 obtained above was deposited and dried in a recess surrounded by a light-shielding partition using a piezo head. The alignment layer was 1.6 μm. Subsequently, the formed alignment layer was rubbed.

(Preparation of optically anisotropic layer)
As the optically anisotropic layer R-1 for R, the coating layer LC-R1 for optically anisotropic layer obtained above has an alignment layer AL-1 surrounded by a light-shielding partition using a piezo head. The droplets were ejected into the recesses and heat-dried and aged at 95 ° C. for 2 minutes to form a layer having a uniform liquid crystal phase. Further, immediately after aging, this layer was irradiated with polarized UV light (illuminance 200 mW / cm ^{2) in} a nitrogen atmosphere with an oxygen concentration of 0.3% or less so that the transmission axis of the polarizing plate was in the TD direction of the transparent support. The amount of irradiation was 200 mJ / cm ² ) to fix the optically anisotropic layer, and an optically anisotropic layer having a thickness of 2.8 μm was formed.
G-use and B-use optical anisotropic layers G-1 and B-1 were formed in the same manner except that LC-G1 and LC-B1 were ejected in place of LC-R1. The optically anisotropic layers of G-1 and B-1 were 2.75 μm and 2.3 μm, respectively.

  In this embodiment, the conveyance speed and the driving frequency are controlled in the portions corresponding to the R, G, and B pixels, and the coating liquid for each optical anisotropic layer is applied to the concave portions corresponding to the desired R, G, and B. I dropped it.

(Preparation of color filter layer)
The PP-R1, PP-G1, and PP-B1, which are liquids for forming the R, G, and B layers obtained above, are placed in a recess surrounded by a light-shielding partition using a piezo head as follows. The droplet was ejected.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm. The head and ink are controlled so that the vicinity of the ejection portion is 40 ± 0.5 ° C. by circulating hot water in the head.

  Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per drop is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed can be set in the range of 50 to 200 mm / s. The piezo drive frequency can be up to 4.6 KHz, and the droplet ejection amount can be controlled by these settings.

In the present embodiment, the parts corresponding to the R, G, and B pixels are transported so that the pigment coating amounts are 1.1, 1.8, and 0.75 g / m ² , respectively. The speed and driving frequency were controlled, and each of the R, G and B layer forming liquids PP-R1, PP-G1 and PP-B1 was ejected into the recesses corresponding to the desired R, G and B.
Thereafter, drying was performed at 100 ° C., and heat treatment was further performed at 240 ° C. for 1 hour to form color filter pixels on the optically anisotropic layer.

(Phase difference measurement)
In-plane retardation Re (0) at an arbitrary wavelength λ and retardation Re (40) when the sample is inclined ± 40 degrees about the slow axis as a rotation axis by the parallel Nicol method using a fiber type spectrometer, Re (−40) was measured. For R, G, and B, λ was measured for retardation of 611 nm, 545 nm, and 435 nm, respectively. For the retardation of the optically anisotropic layer of the present invention, only the retardation of the optically anisotropic layer was obtained by calibrating with the transmittance data of the substrate without the optically anisotropic layer measured in advance. Table 3 shows the phase difference measurement results.

(Formation of transparent electrode)
A transparent electrode film (film thickness of 2000 mm) was formed on the color filter produced above by ITO sputtering.

(Formation of alignment layer and liquid crystal cell formation)
Further, a polyimide alignment film was provided thereon. Next, glass beads having a particle diameter of 5 μm were sprayed. Further, an epoxy resin sealant containing spacer particles is printed at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, and the color filter substrate is applied to the counter substrate at a pressure of 10 kg / cm. Pasted together. Next, the bonded glass substrate was heat-treated at 150 ° C. for 90 minutes to cure the sealing agent, thereby obtaining a laminate of two glass substrates. This glass substrate laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates to obtain a liquid crystal cell. Polarizing plates HLC2-2518 made by Sanritz Co., Ltd. were attached to both surfaces of this liquid crystal cell.

(Production of VA-LCD)
As a cold-cathode tube backlight for a color liquid crystal display device, a phosphor in which BaMg2Al16O27: Eu, Mn and LaPO4: Ce, Tb are mixed at a weight ratio of 50:50 is green (G), and Y2O3: Eu is red (R ), BaMgAl10O17: Eu was blue (B), and a white three-wavelength fluorescent lamp having an arbitrary color tone was produced. A liquid crystal cell provided with the above polarizing plate was placed on the backlight to produce a VA-LCD.

(Production of VA-LCD of Comparative Example 1)
There is no optically anisotropic layer R-1, G-1, or B-1, and instead of the optical film of G-1 using AL-1 and LC-G1 on the protective film on the liquid crystal cell side of the lower polarizing plate. A comparative VA-LCD was produced in the same manner as in Example except that an optically anisotropic layer of 2.75 μm was formed by the same method as that for producing the anisotropic layer.

(Evaluation of VA-LCD)
The viewing angle characteristics of the manufactured liquid crystal display device were measured with a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM). For the examples and comparative examples, the colors on the xy chromaticity diagram when the viewing angle is changed by 0 to 80 degrees in the right direction, the upper right 45 degrees direction, and the upper direction from the front of the LCD in black display (no voltage applied) The results are shown in FIG.

[Example 2]
(Preparation of coating liquid LC-2 for optically anisotropic layer)
The rod-like liquid crystal of the coating liquid LC-R1 for optically anisotropic layer of Example 1 was replaced with the following rod-like liquid crystal (2), and the photopolymerization initiator (LC-1-2) was replaced with the following photopolymerization initiator (LC- Instead of 2-2), methyl ethyl ketone was replaced with chloroform, and a chiral liquid and 4,4′-azoxydianisole were removed to prepare a coating liquid LC-2 for an optically anisotropic layer.

(Preparation of optically anisotropic layer)
In the same manner as in Example 1, the optically anisotropic layer coating liquid LC-2 obtained above was R, G, having an alignment layer AL-1 surrounded by a light-shielding partition using a piezo head. And droplets were ejected into the recesses corresponding to the B layer and heat-dried at 140 ° C. for 2 minutes to form a layer having a uniform liquid crystal phase. Further, immediately after aging, this layer was irradiated with UV light (illuminance 200 mW / cm ² , irradiation amount 1000 mJ / cm ² ) in a nitrogen atmosphere with an oxygen concentration of 0.3% or less to fix the optically anisotropic layer. As a result, an optically anisotropic layer RET-2 having a thickness of 2.9 μm was formed.

(Δn measurement)
The optical anisotropy of the produced optically anisotropic layer RET-2 was measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments), and Δn was determined from the measured value and the film thickness. . The results obtained are shown in the table below.

(Preparation of color filter layer)
It formed in the same manner as Example 1.
(Formation of transparent electrode)
It formed in the same manner as Example 1.

(Formation of alignment layer and liquid crystal cell formation)
Further, a polyimide alignment film was provided thereon. Next, glass beads having a particle diameter of 5 μm were sprayed. Further, an epoxy resin sealant containing spacer particles is printed at a position corresponding to the outer frame of the black matrix provided around the pixel group of the color filter, and the color filter substrate is applied to the counter substrate at a pressure of 10 kg / cm. Pasted together. Next, the bonded glass substrate was heat-treated at 150 ° C. for 90 minutes to cure the sealing agent, thereby obtaining a laminate of two glass substrates. This glass substrate laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates to obtain a liquid crystal cell. A commercially available super high contrast product (manufactured by Sanlitz Co., Ltd., trade name, HLC2-5618) was used for the upper polarizing plate (observer side) of the liquid crystal cell. A polarizing plate HLC2-2518 made by Sanritz was attached to the lower polarizing plate (backlight side).

(Production of VA-LCD)
As a cold-cathode tube backlight for a color liquid crystal display device, a phosphor in which BaMg2Al16O27: Eu, Mn and LaPO4: Ce, Tb are mixed at a weight ratio of 50:50 is green (G), and Y2O3: Eu is red (R ), BaMgAl10O17: Eu was blue (B), and a white three-wavelength fluorescent lamp having an arbitrary color tone was produced. A liquid crystal cell provided with the above polarizing plate was placed on the backlight to produce a VA-LCD.

[Example 3]
Coating liquid LC- prepared by changing the rod-like liquid crystal of the coating liquid LC-2 for optically anisotropic layer to a rod-like liquid crystal represented by the following exemplified compound (provided that x = 4) described in JP-A-2006-64858 A VA-LCD of Example 3 was produced in the same manner as in Example 2 except that 3 was used. The film thicknesses of the optically anisotropic layers R-3 G-3 and B-3 were 1.6 μm, 1.4 μm, and 1.1 μm, respectively.

[Example 4]
The LC-2 rod-like liquid crystal (2) of Example 2 was replaced with Exemplified Compound (II-38) and Exemplified Compound LC-4-1 as “Irgacure 819” (trade name, Ciba Specialty Chemicals) as a polymerization initiator. Using Example Compound (LC-4-2) as an additive and changing the alignment film to polyimide, a VA-LCD of Example 4 was produced.
Specifically, a chloroform 15% solution mixed with 0.4 parts by mass was spin-coated on a glass plate on which a rubbed polyimide alignment film was formed to produce a thin film and heated at a substrate temperature of 110 ° C. Then, after cooling to 77 ° C. at 5 ° C./min, an ultraviolet ray of 1000 mJ / cm ² with an oxygen concentration of 5% or less was irradiated to fix the orientation state of the optically anisotropic layer, and the anisotropic material 31 was produced. When observed under a polarizing microscope, there was almost no defect and the orientation was uniform. The film thicknesses of the optically anisotropic layers R-4 G-4 and B-4 were 0.95 μm, 0.81 μm and 0.66 μm, respectively.

(Evaluation of VA-LCD)
For each of the liquid crystal display devices manufactured in Examples 2 to 4, black display with an azimuth angle of 45 degrees and a polar angle of 60 degrees and a viewing angle of 45 degrees, and an azimuth angle of 45 degrees A color shift of 60 degrees was observed.

  As a result of observing the produced liquid crystal display devices of Examples 2 to 4, it was found that neutral black display was provided in both the front direction and the viewing angle direction.

[Example 5]
(Preparation of coating liquid LC-3 for optically anisotropic layer)
After preparing the following composition, it filtered with the polypropylene filter with the hole diameter of 0.2 micrometer, and obtained coating liquid LC-5.
────────────────────────────────── ――――――
Composition of coating liquid LC-5 (%)
────────────────────────────────── ――――――
Bar-shaped liquid crystal I-2 28.0
Onium salt exemplified compound (58) described in JP-A-2006-106662 0.57
Air interface vertical alignment agent P-27 0.15 described in JP-A-2006-106662
Photopolymerization initiator 1.36
Methyl ethyl ketone 69.92
────────────────────────────────── ――――――

(Preparation of alignment layer)
The alignment layer coating liquid AL-1 obtained above was deposited and dried in a recess surrounded by a light-shielding partition using a piezo head. The alignment layer was 1.6 μm.

(Preparation of the first optical anisotropic layer)
As the optically anisotropic layer R-5 for R, the coating liquid LC-5 for optically anisotropic layer obtained above has an alignment layer AL-1 surrounded by a light-shielding partition using a piezo head. The droplets were ejected into the recesses and heat-dried and aged at 95 ° C for 2 minutes to form a layer having a uniform liquid crystal phase. Further, immediately after aging, this layer was irradiated with UV (illuminance 200 mW / cm ² , irradiation amount 1000 mJ / cm ² ) in a nitrogen atmosphere with an oxygen concentration of 0.3% or less to fix the optically anisotropic layer. Then, an optically anisotropic layer having a thickness of 1.26 μm was formed.
Similarly, G and B optically anisotropic layers G-5 and B-5 were formed. The optically anisotropic layers of G-5 and B-5 were 1.07 μm and 0.85 μm, respectively.

  In this embodiment, the conveyance speed and the driving frequency are controlled in the portions corresponding to the R, G, and B pixels, and the coating liquid LC-3 for the optical anisotropic layer is formed in the concave portions corresponding to the desired R, G, and B. Struck.

(Preparation of color filter layer)
The PP-R1, PP-G1, and PP-B1, which are liquids for forming the R, G, and B layers obtained above, are placed in a recess surrounded by a light-shielding partition using a piezo head as follows. The droplet was ejected.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm. The head and ink are controlled so that the vicinity of the ejection portion is 40 ± 0.5 ° C. by circulating hot water in the head.

  Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per drop is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed can be set in the range of 50 to 200 mm / s. The piezo drive frequency can be up to 4.6 KHz, and the droplet ejection amount can be controlled by these settings.

In the present embodiment, the parts corresponding to the R, G, and B pixels are transported so that the pigment coating amounts are 1.1, 1.8, and 0.75 g / m ² , respectively. The speed and driving frequency were controlled, and each of the R, G and B layer forming liquids PP-R1, PP-G1 and PP-B1 was ejected into the recesses corresponding to the desired R, G and B.
Thereafter, drying was performed at 100 ° C., and heat treatment was further performed at 240 ° C. for 1 hour to form color filter pixels on the first retardation layer.
The average tilt angle of the liquid crystal in the region corresponding to each of the RGB regions was 89.90, and it was confirmed that the rod-like liquid crystal was aligned substantially perpendicular to the substrate. The following table shows the phase difference measurement results of regions R-5, G-5, and B-5 corresponding to the RGB regions.

(Production of IPS mode liquid crystal cell)
A polyimide film was provided on one surface of the glass substrate, and a rubbing treatment was performed to obtain an alignment film.
On a separately prepared glass substrate, electrodes (pixel electrode 2 and display electrode 3 in FIG. 5) are arranged in the liquid crystal element pixel region 1 shown in FIG. 5 so that the distance between adjacent electrodes is 20 μm. Then, a polyimide film was provided as an alignment film thereon, and a rubbing process was performed. The rubbing process was performed in the direction 4 shown in FIG. The two glass substrates are stacked and bonded so that the alignment films face each other, the distance between the substrates (gap; d) is 3.9 μm, and the rubbing directions of the two glass substrates are parallel. A nematic liquid crystal composition having a refractive index anisotropy (Δn) of 0.0769 and a dielectric anisotropy (Δε) of 4.5 was enclosed. The value of d · Δn of the liquid crystal layer was 300 nm. In FIG. 5, 5a and 5b represent directors of the liquid crystal compound during black display, and 6a and 6b represent directors of the liquid crystal compound during white display, respectively.

(Preparation of optically anisotropic film B-1)
<Preparation of cellulose acetate solution>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution A.
<Composition of cellulose acetate solution A>
Cellulose acetate having an acetylation degree of 2.86 100.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass

<Preparation of matting agent dispersion>
20 parts by mass of silica particles having an average particle size of 16 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) and 80 parts by mass of methanol were mixed well for 30 minutes to obtain a silica particle dispersion. This dispersion was put into a disperser together with the following composition, and further stirred for 30 minutes or more to dissolve each component to prepare a mat agent dispersion.
<Matting agent dispersion composition>
Silica particle dispersion with an average particle size of 16 nm 10.0 parts by weight Methylene chloride (first solvent) 76.3 parts by weight Methanol (second solvent) 3.4 parts by weight Cellulose acetate solution A 10.3 parts by weight

<Preparation of additive solution>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

<Additive solution composition>
Compound (A-01) for reducing optical anisotropy 49.3 parts by mass Wavelength dispersion adjusting agent (UV-01) 7.6 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acetate solution A 12.8 parts by mass The Log P value of A-01 is 2.9, respectively.

<Production of cellulose acetate film>
94.6 parts by mass of the cellulose acetate solution A, 1.3 parts by mass of the matting agent solution, and 4.1 parts by mass of the additive solution were mixed after filtration to prepare a dope. In this dope, the mass ratio of the compound for reducing optical anisotropy and the wavelength dispersion adjusting agent to cellulose acetate was 12% and 1.8%, respectively.
The dope was cast on a band using a casting machine, the film was peeled off from the band with a residual solvent amount of 30%, and dried at 140 ° C. for 40 minutes to produce a cellulose acetate film. The obtained cellulose acetate film had a residual solvent amount of 0.2% and a film thickness of 40 μm.

  In this film, Re (630) is 0.3 nm, Rth (630) is 3.2 nm, | Re (400) -Re (700) | is 1.2 nm, and | Rth (400) -Rth (700) | Was 7.5 nm, Tg of the film was 134.3 ° C., haze of the film was 0.34%, and ΔRth (10% RH-80% RH) was 24.9 nm. This film was designated as an optically anisotropic film B-1.

(Preparation of polarizing plate 1 with optically anisotropic film B-1)
A polarizing film is produced by adsorbing iodine to a stretched polyvinyl alcohol film, and using a polyvinyl alcohol adhesive, a commercially available cellulose acetate film (Fuji Film KK, Fujitac TD80UF) is subjected to saponification treatment, Using an alcohol-based adhesive, the polarizing plate 1 was formed by pasting on one side of the polarizing film and pasting the optical anisotropic film B-1 on the other side.

(Preparation of polarizing plate 2 with second optically anisotropic layer (positive A-plate))
An adhesive is applied to the optical anisotropic film B-1 side of the polarizing plate 1 with the optical anisotropic film B-1, and a positive a-plate polycarbonate film (Re (550 nm) = 133.77 nm on the adhesive surface. , Re (450 nm) / Re (550 nm) = 0.996, Re (650 nm) / Re (550 nm) = 1.053) so that the slow axis direction is perpendicular to the transmission axis of the polarizing film. A polarizing plate 2 with an a-plate was formed.
The phase difference at the R, G and B wavelengths of the positive A-plate used was measured. The results are shown in the table below.

(Production of IPS-LCD)
In one of the IPS mode liquid crystal cells produced above, the transmission axis of the polarizing film of the polarizing plate 1 is parallel to the rubbing direction of the liquid crystal cell, and the optically anisotropic film B-1 side is on the liquid crystal cell side. Pasted. Subsequently, on the other side of the IPS mode liquid crystal cell, the polarizing plate 2 is placed so that the slow axis of the positive A-plate polycarbonate film is parallel to the rubbing direction of the liquid crystal cell and the polycarbonate film side is on the liquid crystal cell side. A liquid crystal display device was manufactured by pasting the film as described above.

[Example 6]
(Preparation of optically anisotropic layer)
Recesses corresponding to the R, G, and B layers on the glass substrate surrounded by the light-shielding partition using the piezo-type head for the optically anisotropic layer coating liquid LC-5 in the same manner as in Example 3. And aged by heating and drying at 80 ° C. for 1 minute to form a layer having a uniform liquid crystal phase. Immediately after aging, this layer was irradiated with UV light (illuminance 200 mW / cm 2, irradiation amount 1000 mJ / cm 2) in a nitrogen atmosphere with an oxygen concentration of 0.3% or less to fix the optically anisotropic layer, Optically anisotropic layers R-4, G-4, and B-4 were produced. The transport speed and drive frequency were controlled so that the thicknesses of R-6, G-6, and B-6 were 1.26 μm, 1.07 μm, and 0.85 μm, respectively. The average tilt angle of the liquid crystal was 89.9 °, and it was confirmed that the rod-like liquid crystal was aligned substantially perpendicular to the substrate.

(Preparation of color filter layer)
It formed in the same manner as Example 1.

(Production of IPS mode liquid crystal cell)
A polyimide film was provided on one surface of the glass substrate, and a rubbing treatment was performed to obtain an alignment film.
On a separately prepared glass substrate, electrodes (pixel electrode 2 and display electrode 3 in FIG. 5) are arranged in the liquid crystal element pixel region 1 shown in FIG. 5 so that the distance between adjacent electrodes is 20 μm. Then, a polyimide film was provided as an alignment film thereon, and a rubbing process was performed. The rubbing process was performed in the direction 4 shown in FIG. The two glass substrates are stacked and bonded so that the alignment films face each other, the distance between the substrates (gap; d) is 3.9 μm, and the rubbing directions of the two glass substrates are parallel. A nematic liquid crystal composition having a refractive index anisotropy (Δn) of 0.0769 and a dielectric anisotropy (Δε) of 4.5 was enclosed. The value of d · Δn of the liquid crystal layer was 300 nm. In FIG. 5, 5a and 5b represent directors of the liquid crystal compound during black display, and 6a and 6b represent directors of the liquid crystal compound during white display, respectively.

(Production of IPS-LCD)
In one of the IPS mode liquid crystal cells produced above, the transmission axis of the polarizing film of the polarizing plate 1 is parallel to the rubbing direction of the liquid crystal cell, and the optically anisotropic film B-1 side is on the liquid crystal cell side. Pasted. Subsequently, on the other side of the IPS mode liquid crystal cell, the polarizing plate 2 is placed so that the slow axis of the positive A-plate polycarbonate film is parallel to the rubbing direction of the liquid crystal cell and the polycarbonate film side is on the liquid crystal cell side. A liquid crystal display device was manufactured by pasting the film as described above.

[Example 7]
<Preparation of optically anisotropic layer>
The optical anisotropic films R-7, G-7, and B-7 were prepared in the same manner as the optical anisotropic films R-5, G-5, and B-5 of Example 5 except that the film thickness was changed. Were prepared.
The retardation of the formed layer was measured. The results are shown in the table below.

<Preparation of color filter layer>
The same operation as in Example 5 was performed.
<Production of IPS liquid crystal mode cell>
It was produced in the same manner as in Example 5.

<Production of second optically anisotropic layer (biaxial film)>
Put the following composition into the mixing tank, stir while heating, dissolve each component,
A cellulose acetate solution was prepared. The solution was filtered using a filter paper (No. 63, manufactured by Advantech) having a retained particle diameter of 4 μm and a drainage time of 35 seconds at 0.5 MPa (5 kg / cm ² ) or less.

───────────────────────────────────────
Cellulose acetate solution composition ───────────────────────────────────────
Cellulose acetate having an acetylation degree of 60.9% (degree of polymerization: 300, Mn / Mw = 1.5) 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) 54 parts by weight 1-butanol (third solvent) 11 parts by weight ──────────────────── ───────────────────

  In another mixing tank, 8 parts by mass of the following retardation increasing agent A, 10 parts by mass of retardation increasing agent B, 0.28 parts by mass of silicon dioxide fine particles (average particle size: 0.1 μm), 80 parts by mass of methylene chloride And 20 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution (and a fine particle dispersion). The dope was prepared by mixing 474 parts by mass of the cellulose acetate solution with 40 parts by mass of the retardation increasing agent solution and stirring sufficiently.

  The obtained dope was cast using a band casting machine. A film having a residual solvent amount of 15% by mass was stretched transversely at a stretch ratio of 20% using a tenter under the conditions of 130 ° C., held at 50 ° C. for 30 seconds with the stretched width, and then clipped to remove cellulose. An acetate film was prepared. The residual solvent amount at the end of stretching was 5% by mass, and further dried to prepare a second optical anisotropic layer B-2 with the residual solvent amount being less than 0.1% by mass.

  The thickness of the second optically anisotropic layer B-2 thus obtained was 80 μm. About the produced 2nd optically anisotropic layer B-2, Re and Rth in the wavelength of R, G, and B were used using an automatic birefringence meter (KOBRA-21ADH, Oji Scientific Instruments Co., Ltd. product). It was measured. The results are shown in the table below.

<Preparation of Polarizing Plate 3 with Second Optically Anisotropic Layer (Biaxial Film)>
A polarizing film is produced by adsorbing iodine to a stretched polyvinyl alcohol film, and using a polyvinyl alcohol adhesive, a commercially available cellulose acetate film (Fuji Film KK, Fujitac TD80UF) is subjected to saponification treatment, Using an alcohol-based adhesive, the polarizing film 3 was formed by pasting on one side of the polarizing film and pasting the second optical anisotropic layer B-2 on the other side.

(Production of IPS-LCD)
In one of the IPS mode liquid crystal cells produced above, the transmission axis of the polarizing film of the polarizing plate 1 is parallel to the rubbing direction of the liquid crystal cell, and the optically anisotropic film B-1 side is on the liquid crystal cell side. Pasted. Subsequently, the polarizing plate 3 is placed on the other side of the IPS mode liquid crystal cell so that the slow axis is parallel to the rubbing direction of the liquid crystal cell, the second optically anisotropic layer B-2, and the biaxial film. Were attached so as to be on the liquid crystal cell side, and a liquid crystal display device was produced.

[Example 8]
(Preparation of coating liquid AL-8 for alignment layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as coating liquid AL-8 for alignment layer.
Composition of Alignment Film Coating Solution Modified Polyvinyl Alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 part by weight Paratoluenesulfonic acid 0.3 part by weight

(Preparation of coating liquid LC-8 for optically anisotropic layer)
1.8 g of the following discotic liquid crystalline compound, 0.2 g of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 0 0.06 g, 0.02 g of sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), and 0.01 g of air interface side vertical alignment agent (Exemplary Compound P-6) described in JP-A-2005-222004. Dissolved in 9 g of methyl ethyl ketone was used as coating liquid LC-8 for optically anisotropic layer.

(Preparation of alignment layer)
The alignment layer coating liquid AL-8 obtained above was ejected onto a recess surrounded by a light-shielding partition and dried using a piezo-type head. Subsequently, the formed alignment layer was rubbed to prepare an alignment layer AL-8.

(Preparation of optically anisotropic layer)
As the optically anisotropic layer R-8 for R, the coating layer LC-8 for optically anisotropic layer obtained above has an alignment layer AL-8 surrounded by a light-shielding partition wall using a piezoelectric head. The droplets were ejected into the recesses and heat-dried at 125 ° C. for 3 minutes to form a layer having a uniform liquid crystal phase. Further, immediately after aging, this layer was irradiated with UV (illuminance 200 mW / cm ² , irradiation amount 2000 mJ / cm ² ) in a nitrogen atmosphere with an oxygen concentration of 0.3% or less to fix the optically anisotropic layer. An optically anisotropic layer was formed.
Similarly, G and B optically anisotropic layers G-8 and B-8 were formed. The transport speed and drive frequency were controlled so that Re / Rth of R-8, G-8, and B-8 were 136 nm / −67 nm, 115 nm / −57 nm, and 94 nm / −47 nm, respectively. The average tilt angle of the liquid crystal was 89.9 °, and it was confirmed that the discotic liquid crystal was aligned substantially perpendicular to the film surface.

(Preparation of color filter layer)
It formed in the same manner as Example 1.

(Production of IPS mode liquid crystal cell)
A polyimide film was provided on one surface of the glass substrate, and a rubbing treatment was performed to obtain an alignment film.
On a separately prepared glass substrate, electrodes (pixel electrode 2 and display electrode 3 in FIG. 5) are arranged in the liquid crystal element pixel region 1 shown in FIG. 5 so that the distance between adjacent electrodes is 20 μm. Then, a polyimide film was provided thereon as an alignment film, and a rubbing process was performed. The rubbing process was performed in the direction 4 shown in FIG. The two glass substrates are stacked and bonded so that the alignment films face each other, the distance between the substrates (gap; d) is 3.9 μm, and the rubbing directions of the two glass substrates are parallel. A nematic liquid crystal composition having a refractive index anisotropy (Δn) of 0.0769 and a dielectric anisotropy (Δε) of 4.5 was enclosed. The value of d · Δn of the liquid crystal layer was 300 nm. In FIG. 5, 5a and 5b represent directors of the liquid crystal compound during black display, and 6a and 6b represent directors of the liquid crystal compound during white display, respectively.

(Preparation of optical compensation film 8)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution having the following composition.
Composition of cellulose acetate solution Cellulose acetate with an acetylation degree of 60.9% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 Mass part Methanol (second solvent) 54 parts by mass 1-butanol (third solvent) 11 parts by mass In another mixing tank, 16 parts by mass of the following retardation increasing agent, 80 parts by mass of methylene chloride, and 20 parts by mass of methanol were added. Then, the mixture was stirred while heating to prepare a retardation increasing agent solution. A dope was prepared by mixing 7 parts by mass of the retardation increasing agent solution with 487 parts by mass of the cellulose acetate solution and stirring sufficiently.

Retardation raising agent

  The obtained dope was cast using a band casting machine. After the film surface temperature on the band reached 40 ° C., the film was dried with warm air of 60 ° C. for 1 minute, and the film was peeled off from the band. Next, the film was dried with a drying air at 140 ° C. for 10 minutes to produce a cellulose acetate film 1 having a thickness of 80 μm.

  The optical properties of this film were measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments), and found to be Re = 8 nm and Rth = 82 nm.

(Production of IPS-LCD)
A polarizing film was produced by adsorbing iodine to a stretched polyvinyl alcohol film. The produced optical compensation film 8 was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizing film and the slow axis of the optical compensation film were arranged in parallel. A commercially available cellulose acetate film (Fujitac TD80UF, manufactured by Fuji Film Co., Ltd., thickness 80 μm, Re = 3 nm, Rth = 45 nm) is saponified and attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive. I attached. This was affixed to one of the IPS mode liquid crystal cells produced above so that the slow axis of the optical compensation film 8 was parallel to the rubbing direction of the liquid crystal cell. Subsequently, a commercially available polarizing plate (HLC2-5618, manufactured by Sanritz Co., Ltd.) was attached to the other side of the IPS mode liquid crystal cell 1 in a crossed Nicol arrangement to produce a liquid crystal display device.

[Example 9]
According to the method described in JP-A-2006-64858, an IPS-LCD having a positive C-plate and a positive A-plate on a colored layer was produced.
[Comparative Example 2]
An IPS mode liquid crystal display device was manufactured by the same method as described in Examples 3 and 4 of JP-A-2006-78647.

<LCD evaluation for warping>
The liquid crystal display devices produced in Examples 5 to 9 and Comparative Example 2 were left for 50 hours in an environment with a temperature of 50 ° C. and a relative humidity of 95%, and then taken out into an environment with a temperature of 25 ° C. and a relative humidity of 60%. After 5 minutes from the removal, the power was turned on, the liquid crystal cell was removed from the liquid crystal display device, and the warpage amount W (mm) was measured. The warpage amount w (mm) was defined as a positive value for the warpage concave in the front direction of the substrate and a negative value for the warpage amount convex in the front direction of the substrate. The amount of warpage was measured from the average value of the displacement of the corners of the panel 4 and the center of the panel using a CCD laser displacement meter (LK-85 manufactured by Keyence).
In the liquid crystal cells of Examples 5 to 9, no warpage was measured, but in Comparative Example 2, the warpage was measured by 5 mm.

<LCD evaluation for viewing angle characteristics>
Table 10 shows the results of visual evaluation of viewing angle characteristics of the liquid crystal display devices manufactured in Examples 5 to 9 and Comparative Example 2.

It is a schematic diagram which shows an example of the flow of the manufacturing method of this invention. It is a schematic sectional drawing of an example of the board | substrate which the liquid crystal display device of this invention has. It is a schematic sectional drawing of an example of the liquid crystal display device of this invention. It is a figure which shows the color viewing angle characteristic of VA-LCD produced by the Example and the comparative example. It is the schematic which shows the pixel area example of the liquid crystal cell produced in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal element pixel area 2 Pixel electrode 3 Display electrode 4 Rubbing direction 5a, 5b Liquid crystal compound director 6a, 6b at the time of black display Liquid crystal compound director 11 at the time of white display Transparent substrate 12 Black matrix (partition wall)
13 Optically anisotropic layer 14 Color filter layer 21 Transfer substrate 22 Black matrix (partition wall)
23 Color filter layer 24 Solid optical anisotropic layer 25 Transparent electrode layer 26 Alignment layer 27 Patterning optical anisotropic layer 31 Liquid crystal 32 TFT
33 Polarizing layer 34 Cellulose acetate film (polarizing plate protective film)
35 Cellulose acetate film or optical compensation sheet 36 Polarizing plate 37 Liquid crystal cell

Claims (30)

A liquid crystal display device in which liquid crystal is sandwiched between a first substrate and a second substrate, wherein the first substrate has a pattern layer patterned in a fine region, and the pattern layer is a substrate normal line A liquid crystal display device comprising a color filter layer and a first optical anisotropic layer laminated in a direction, and a partition wall formed at a boundary portion of each pattern layer. The liquid crystal display device according to claim 1, wherein the fine regions are arranged in a matrix. The optically anisotropic layer is a layer formed by applying and drying a fluid containing a liquid crystal compound having at least one reactive group to form a liquid crystal phase, and then immobilizing by irradiation with heat or ionizing radiation. 3. A liquid crystal display device according to 1 or 2. The liquid crystal display device according to claim 3, wherein the ionizing radiation is ultraviolet rays. The liquid crystal display device according to claim 3, wherein the reactive group is an ethylenically unsaturated group. The liquid crystal display device according to claim 3, wherein the fluid further contains at least one radical polymerization initiator. The liquid crystal display device according to claim 3, wherein the liquid crystal compound is a rod-like liquid crystal. The liquid crystal display device according to claim 7, wherein the rod-like liquid crystal is a rod-like liquid crystal that exhibits a smectic A phase. The liquid crystal display according to claim 7, wherein the rod-like liquid crystal exhibits a nematic phase or a smectic A phase, and an intrinsic birefringence Δn (λ) at a wavelength λ of the liquid crystal phase satisfies the following formulas (I) and (II): apparatus:
Formula (I): Δn (450 nm) / Δn (550 nm) <1
Formula (II): Δn (650 nm) / Δn (550 nm)> 1. The liquid crystal display device according to claim 3, wherein the liquid crystal compound is a discotic liquid crystal compound. The liquid crystal display device according to claim 3, wherein the first optically anisotropic layer contains molecules of a discotic liquid crystalline compound fixed in a substantially vertical alignment state. The liquid crystal display device according to claim 3, wherein the liquid crystal phase is a cholesteric phase. The in-plane retardation (Re) of the first optically anisotropic layer is not 0, and the first optically anisotropic layer is a layer surface method with an in-plane slow axis as the tilt axis (rotation axis). A retardation value measured by making light having a wavelength λ nm incident from a direction inclined by + 40 ° with respect to the line direction, and −40 with respect to the normal direction of the layer surface with the in-plane slow axis as the inclination axis (rotation axis) The liquid crystal display device according to claim 1, wherein the liquid crystal display device has a biaxial property in which retardation values measured by making light having a wavelength of λ nm incident from an inclined direction are substantially equal. The first optically anisotropic layer has an in-plane retardation (Re) of 15 to 200 nm, an in-plane slow axis as an inclination axis (rotation axis), and a direction inclined + 40 ° with respect to the normal direction of the layer surface. The light having the wavelength λ nm is incident from the direction inclined by −40 ° with respect to the normal direction of the layer surface with the retardation value measured by making the light having the wavelength λ nm incident and the in-plane slow axis as the tilt axis (rotation axis) The liquid crystal display device according to any one of claims 1 to 13, wherein the retardation values measured in the above are substantially equal and the values are 50 to 250 nm. The liquid crystal display device according to claim 1, wherein the optically anisotropic layer is formed on a rubbing-treated surface of the alignment layer. 16. The liquid crystal display device according to claim 1, further comprising a second optically anisotropic layer composed of one layer continuous with the first substrate or the second substrate. The liquid crystal display device according to claim 16, wherein the first optically anisotropic layer is a positive A plate, the second optically anisotropic layer is a negative C plate, and the display mode is a VA mode. . The color filter layer includes an R region, a G region, and a B region, and an in-plane retardation of the region of the first optically anisotropic layer disposed on or below the R, G, and B regions, 18. The liquid crystal display according to claim 17, wherein Re (R layer)> Re (G layer)> Re (B layer) satisfying Re (R layer), Re (G layer), and Re (B layer), respectively. apparatus. The liquid crystal display device according to claim 16, wherein the first optical anisotropic layer is a positive C plate, the second optical anisotropic layer is a positive A plate, and the display mode is an IPS mode. . The liquid crystal display device according to claim 19, wherein the retardation Re (λ) of the positive A-plate at a wavelength λ satisfies the following formulas (III) and (IV):
(III): Re (450 nm) / Re (550 nm) <1
(IV): Re (650 nm) / Re (550 nm)> 1. The first optically anisotropic layer is a positive C plate, the in-plane retardation (Re) of the second optically anisotropic layer is not 0, and the in-plane slow axis is an inclined axis (rotation) Axis), the retardation value measured by making light of wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the layer surface, and the normal of the layer surface with the in-plane slow axis as the tilt axis (rotation axis) The liquid crystal display according to claim 16, wherein the retardation value measured by making light having a wavelength of λ nm incident from a direction inclined by -40 ° with respect to the direction is substantially biaxial, and the display mode is an IPS mode. apparatus. Retardation Re (550) at a wavelength of 550 nm of the second optical anisotropic layer region is 20 nm to 150 nm, in-plane refractive indexes nx and ny (nx> ny), and refractive index nz in the thickness direction The Nz value at a wavelength of 550 nm of the second optically anisotropic layer region defined by Nz = (nx−nz) / (nx−ny) is 1.5 to 7 according to claim 16 or 21. Liquid crystal display device. The method for manufacturing a liquid crystal display device according to any one of claims 1 to 22, comprising at least the following steps [1] to [4] in this order:
[1] A step of forming a plurality of partition walls on the surface of the first substrate and forming fine regions separated by the partition walls,
[2] A fluid containing at least one liquid crystalline compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet type discharge head to the fine region at a predetermined position and dried to form a liquid crystal phase. A step of exposing to form an optically anisotropic layer;
[3] A step of laminating a color filter layer on the optically anisotropic layer by ejecting and drying a color filter ink liquid from an ink jet type ejection head;
[4] A step of bonding the first substrate and the second substrate together. The method for manufacturing a liquid crystal display device according to any one of claims 1 to 22, comprising at least the following steps [1] to [4] in this order:
[1] A step of forming a plurality of partition walls on the surface of the first substrate and forming fine regions separated by the partition walls,
[2] A step of forming a color filter layer by discharging and drying a color filter ink liquid from an inkjet discharge head to the fine region at a predetermined position;
[3] On the color filter layer, a fluid containing at least one liquid crystal compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet discharge head and dried to form a liquid crystal phase. Then, exposing and laminating an optically anisotropic layer,
[4] A step of bonding the first substrate and the second substrate together. 24. The method further comprises the step of forming an alignment layer and rubbing the surface of the layer before the step of discharging the fluid containing the at least one liquid crystalline compound and exhibiting a predetermined optical anisotropy. Or the method according to 24. A pattern layer patterned in a fine region on a substrate, the pattern layer including a color filter layer and an optically anisotropic layer laminated in a normal direction of the substrate, and a partition wall at a boundary portion of each pattern layer A color filter substrate formed. 27. The color filter substrate according to claim 26, comprising a color filter layer and an optically anisotropic layer in this order on the substrate. 27. The color filter substrate according to claim 26, comprising an optically anisotropic layer and a color filter layer in this order on the substrate. A method for producing a color filter substrate including at least the following steps [1] to [3] in this order:
[1] A step of forming a plurality of partitions on the surface of the substrate and forming a fine region separated by the partitions,
[2] A fluid containing at least one liquid crystalline compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet type discharge head to the fine region at a predetermined position and dried to form a liquid crystal phase. A step of exposing to form an optically anisotropic layer;
[3] A step of laminating a color filter layer on the optically anisotropic layer by discharging and drying a color filter ink liquid from an inkjet discharge head. A method for producing a color filter substrate including at least the following steps [1] to [3] in this order:
[1] A step of forming a plurality of partition walls on the surface of the first substrate and forming fine regions separated by the partition walls,
[2] A step of forming a color filter layer by discharging and drying a color filter ink liquid from an inkjet discharge head to the fine region at a predetermined position;
[3] On the color filter layer, a fluid containing at least one liquid crystal compound and exhibiting a predetermined optical anisotropy is discharged from an ink jet discharge head and dried to form a liquid crystal phase. Then, the process of exposing and laminating | stacking an optically anisotropic layer.

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