JP4975467B2 - Optical element, transflective liquid crystal display device, and transfer material - Google Patents

Description

  The present invention relates to an optical element used in a liquid crystal display device, a transflective liquid crystal display device, and a transfer material useful for the production thereof.

  In recent years, transflective liquid crystal display devices with high outdoor visibility and low power consumption have been used for display devices for mobile electronic devices such as mobile phones, portable music players, and personal digital assistants (PDAs). Attention has been paid. This liquid crystal display device is provided with a reflection portion that performs display by reflecting incident light from the outside with a reflector and a transmission portion that performs display by switching light from a backlight. High visibility even in intense sunlight, vivid display is possible even in dark indoors, and power consumption can be saved by turning off the backlight when it is not needed, so it is longer than transmissive liquid crystal display devices There is an advantage that time driving becomes possible.

The basic configuration of a transflective liquid crystal display device is disclosed in, for example, Patent Documents 1 and 2 below.
Conventional transflective liquid crystal display devices are generally formed on one opposing surface of a pair of liquid crystal cell substrates with a reflective electrode formed of a highly reflective material and a highly transparent material. A transparent electrode, a counter electrode on the opposite surface of the other substrate, and a liquid crystal layer made of a liquid crystal material between the reflective electrode and the transparent electrode and the counter electrode. A λ / 4 plate, a λ / 2 plate, and a polarizing plate are laminated in this order on the surface opposite to the facing surface of the substrate having the reflective electrode and the transparent electrode.

In the liquid crystal display device having the above configuration, a reflective display is realized by providing a λ / 4 layer as a retardation layer on the entire surface on the substrate side serving as a display surface. On the other hand, when transmissive display is realized, a retardation layer such as a λ / 4 layer is not necessary, but a λ / 4 layer exists on the entire surface on the substrate side serving as a display surface for reflective display. In order to compensate for the phase difference in the λ / 4 layer, it is necessary to use the λ / 4 layer on the rear substrate side. In other words, although there is a λ / 4 layer on the display surface for reflection display, which is originally unnecessary for transmissive display, one sheet must be added on the rear surface to compensate for this phase difference. It was. The λ / 2 layer is also provided on both sides, but this is also necessary for suppressing hue change due to the influence of wavelength dispersion of the λ / 4 layer, and is optimal for each of R, G, and B colors. This is because it was difficult to provide a simple λ / 4 layer. These polarizing plates, λ / 2 layers, and λ / 4 layers have different optical axis directions when they are bonded together, and cannot be mass-produced by roll-to-roll, and are stacked one by one after being cut into small pieces. , Productivity is getting very bad.
As described above, the conventional transflective liquid crystal display device uses a larger number of retardation layers than the reflective liquid crystal display device and the transmissive liquid crystal display, which increases costs and increases the thickness of the cell. Have inconvenient problems.

A method for solving such a problem by forming a retardation layer on the inner side (in-cell) of a substrate has been proposed (Patent Document 3). In this method, by providing an optimized λ / 4 layer in a pattern, it is possible to eliminate the extra λ / 2 layer and λ / 4 layer by providing the necessary phase difference only in the region corresponding to the reflective portion. It is shown. Patent Document 3 discloses that an optimal λ / 4 layer is formed by patterning using a liquid crystal compound as a material and utilizing a photolithography method.
JP 2000-29010 A JP 2000-35570 A JP 2003-322857 A

  However, the method described in Patent Document 3 has a problem in that color misregistration due to the wavelength dispersion characteristics of the λ / 4 layer retardation occurs. As a method for solving this problem, a method of patterning a λ / 4 layer having an optimum retardation for each of R, G, and B has also been proposed, but this requires a number of steps. was there. For example, when forming an optimal λ / 4 layer for each of R, G, and B, alignment layer formation (alignment material application, baking, rubbing), liquid crystal compound formation (liquid crystal compound application, alignment baking), patterning ( The process of resist coating, exposure, alkali development, baking, solvent development) is repeated for each of R, G, and B colors in the reflection region and the transmission region, so that each of the R, G, and B colors is further transmitted twice. In the case where the retardation layer is also provided in the part, a total of six optical anisotropic layer forming steps must be performed, which causes a problem of an increase in cost.

The present invention solves such problems, and provides a transflective liquid crystal display device which can be easily manufactured with a small number of steps and has good display characteristics, and an optical element useful for such a liquid crystal display device. This is the issue.
Another object of the present invention is to provide a transfer material useful for producing the transflective liquid crystal display device and optical elements.

Means for solving the above problems are as follows.
[1] Patterned into an arbitrary shape, containing a compound represented by the following general formula (I) or general formula (II), or derived from a compound represented by the following general formula (I) or (II) An optical element having an optically anisotropic layer containing a polymer containing a repeating unit:

式中、Ｌ¹及びＬ²は各々独立に単結合又は二価の連結基を表し；Ａ¹及びＡ²は各々独立に、−Ｏ−、−ＮＲ−（Ｒは水素原子又は置換基を表す）、−Ｓ−及び−ＣＯ−からなる群から選ばれる基を表し；Ｒ¹、Ｒ²、及びＲ³は各々独立に置換基を表し；Ｘは第１４〜１６族の非金属原子を表し、ただし、Ｘには水素原子又は置換基が結合してもよく；ｎは０〜２の整数を表し； Formula (I)

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represents a substituent; X represents a non-metallic atom of Groups 14-16 Provided that a hydrogen atom or a substituent may be bonded to X; n represents an integer of 0 to 2;

式中、ＭＧ¹及びＭＧ²はそれぞれ独立に、２〜８個の環状基から構成される液晶相の発現を誘起する液晶コア部であり、液晶コア部を構成する環状基としては、芳香族環、脂肪族環、及び複素環のいずれでもよく；ＭＧ¹及びＭＧ²を構成する環状基の１つは、Ｌ¹¹及びＬ¹²で置換され；Ｒ¹¹、Ｒ¹²、Ｒ¹³、及びＲ¹⁴はそれぞれ液晶コア部の分子長軸方向に置換している液晶相の発現を誘起する柔軟性のある置換基、双極子作用基及び水素結合性基であり；Ｌ¹¹及びＬ¹²はそれぞれ独立に、液晶コア部ＭＧ¹及びＭＧ²に置換する連結基であり、下記式（ＩＩ）−ＬＡ又は式（ＩＩ）−ＬＢで表され； Formula (II)

In the formula, MG ¹ and MG ² are each independently a liquid crystal core part that induces the expression of a liquid crystal phase composed of 2 to 8 cyclic groups, and the cyclic group constituting the liquid crystal core part is an aromatic group Any of a ring, an aliphatic ring, and a heterocyclic ring; ^one of the cyclic groups constituting MG ¹ and MG ² is substituted with L ¹¹ and L ¹² ; R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ Are flexible substituents, dipole action groups, and hydrogen bonding groups that induce the expression of the liquid crystal phase substituted in the molecular long axis direction of the liquid crystal core; L ¹¹ and L ¹² are each independently , A linking group substituted on the liquid crystal core parts MG ¹ and MG ² , represented by the following formula (II) -LA or formula (II) -LB;

Formula (II) -LA

式中、＊はＭＧ¹を構成する環状基に置換する位置を表し；＃はＰ¹と連結する位置を表し；Ａ¹¹、Ａ¹³及びＡ¹⁴はそれぞれ独立に、―Ｏ−、−ＮＨ−、−Ｓ−、−ＣＨ₂−、−ＣＯ−、−ＳＯ−、又は−ＳＯ₂−を表し；Ａ¹²は−ＣＨ＝又は−Ｎ＝を表し；Ｌ¹¹及びＬ¹²の双方が式（ＩＩ）−ＬＡで表される基の場合、置換基Ｐ¹は単結合、又は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、１，４−フェニレン及びそれらの組み合わせからなる群より選ばれる二価の連結基を表し；Ｌ¹¹及びＬ¹²の一方が、式（ＩＩ）−ＬＢで表される基で、他方が式（ＩＩ）−ＬＡで表される基の場合、置換基Ｐ¹は、＊＝ＣＨ−Ｐ¹¹−＃、又は＊＝Ｎ−Ｐ¹¹−＃で表され（＊は式（ＩＩ）−ＬＢで表される基との連結位置を表し、＃は式（ＩＩ）−ＬＡで表される基との連結位置を表す）；Ｐ¹¹は単結合、又は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、１，４−フェニレン及びこの組み合わせから選ばれる二価の連結基を表し；Ｌ¹¹及びＬ¹²の双方が式（ＩＩ）−ＬＢで表される基の場合、置換基Ｐ¹は、二重結合、＝ＣＨ−Ｐ¹¹−ＣＨ＝、＝Ｎ−Ｐ¹¹−ＣＨ＝、＝Ｎ−Ｐ¹¹−Ｎ＝を表し；Ｐ¹¹は上記Ｐ¹¹と同義である。 Formula (II) -LB

In the formula, * represents a position substituted with the cyclic group constituting MG ¹ ; # represents a position linked to P ¹ ; A ¹¹ , A ¹³ and A ¹⁴ are each independently —O—, —NH—. , -S-, -CH _2- , -CO-, -SO-, or -SO _2- ; A ¹² represents -CH = or -N =; both L ¹¹ and L ¹² are represented by the formula (II ) In the case of a group represented by -LA, the substituent P ¹ is a single bond or a divalent group selected from the group consisting of -CH = CH-, -C≡C-, 1,4-phenylene and combinations thereof. In the case where one of L ¹¹ and L ¹² is a group represented by the formula (II) -LB and the other is a group represented by the formula (II) -LA, the substituent P ¹ is represented by * = CH-P ¹¹ - #, or * = N-P ¹¹ - represented by # (* represents a linking position between the groups of the formula (II) -LB, # in formula (II) -LA Group represented Represents the coupling position); P ¹¹ is a single bond, or a -CH = CH -, - C≡C-, represents a 1,4-phenylene and a divalent linking group selected from the combination; L ¹¹ and L ¹² Are both groups represented by the formula (II) -LB, the substituent P ¹ is a double bond, ═CH—P ¹¹ —CH═, ═N—P ¹¹ —CH═, ═N—P ^11. -N =; P ¹¹ has the same meaning as P ¹¹ above.

[2] The optically anisotropic layer has a phase difference Δnd (450 nm) measured at a wavelength of 450 nm, a phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a phase difference Δnd (650 nm) measured at a wavelength of 650 nm. The optical element according to [1], wherein Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm).
[3] The optical element according to [1] or [2], wherein the optically anisotropic layer is a layer transferred from a transfer material.
[4] A liquid crystal composition in which the optically anisotropic layer contains at least one compound represented by the general formula (I) or the general formula (II) is ejected from the ink jet type ejection head to the surface, thereby producing a liquid crystal. The optical element according to [1] or [2], wherein the optical element is a layer formed by exposing and curing the composition after forming a phase.
[5] After the optically anisotropic layer is coated on the surface with a liquid crystal composition containing at least one compound represented by the general formula (I) or the general formula (II) to form a liquid crystal phase, The optical element according to [1] or [2], wherein the optical element is a layer formed through an exposure step and a development step.

[6] A transflective liquid crystal display device having an optically anisotropic layer patterned into an arbitrary shape, wherein the optically anisotropic layer comprises a compound represented by the general formula (I) or (II) A transflective liquid crystal display device comprising a layer containing or a polymer containing a repeating unit derived from the compound represented by formula (I) or (II).
[7] The optically anisotropic layer has a phase difference Δnd (450 nm) measured at a wavelength of 450 nm, a phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a phase difference Δnd (650 nm) measured at a wavelength of 650 nm. The transflective liquid crystal display device according to [6], wherein Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm).
[8] The transflective liquid crystal display device according to [6] or [7], wherein the optically anisotropic layer is a λ / 4 plate.
[9] It has a pair of transparent substrates and a liquid crystal layer disposed between the pair of substrates, and the optically anisotropic layer is provided inside one of the pair of transparent substrates. The transflective liquid crystal display device according to any one of [6] to [8].
[10] The transflective liquid crystal display device according to any one of [6] to [9], comprising a reflective region and a transmissive region, wherein the optically anisotropic layer is formed in the reflective region .
[11] The transflective liquid crystal display device according to any one of [6] to [10], wherein the optically anisotropic layer is uniaxial or biaxial.
[12] Any one of [6] to [11], wherein the optically anisotropic layer has an optical axis of extraordinary light in an in-plane direction or in a direction perpendicular to the plane. Transflective liquid crystal display device.
[13] The transflective liquid crystal display device according to any one of [6] to [13], further including at least one viewing angle compensation layer.
[14] A pair of transparent substrates, a liquid crystal layer disposed between the pair of substrates, a reflective layer on one surface of the pair of transparent substrates, and the reflective layer of the transparent substrate [13] The transflective liquid crystal display device according to [13], wherein the viewing angle compensation layer is provided on a surface opposite to the surface having the liquid crystal.
[15] In the above [13] or [14], the viewing angle compensation layer has a layer formed by polymerizing a polymerizable composition containing a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound. Transflective liquid crystal display device.
[16] The transflective liquid crystal display device according to any one of [6] to [15], wherein the liquid crystal mode is an ECB, TN, IPS, VA, or OCB mode.
[17] A support and a compound containing the compound represented by the general formula (I) or (II) on the support or derived from the compound represented by the general formula (I) or (II) A transfer material having an optically anisotropic layer containing a polymer containing a repeating unit and at least one photosensitive resin layer.

[18] The optically anisotropic layer has a phase difference Δnd (450 nm) measured at a wavelength of 450 nm, a phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a wavelength of 650 nm in the wavelength region of visible light. The transfer material according to [17], wherein the phase difference Δnd (650 nm) satisfies Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm).
[19] The transfer material according to [17] or [18], wherein the optically anisotropic layer is a λ / 4 plate.
[20] The transfer material according to any one of [17] to [18], wherein the optically anisotropic layer is uniaxial or biaxial.
[21] The transfer material according to any one of [17] to [20], wherein the optically anisotropic layer is a layer having an optical axis of extraordinary light in an in-plane direction or in a direction perpendicular to the surface.
[22] The transfer material according to any one of [17], wherein the optically anisotropic layer is a layer having no optical axis.
[23] From the direction in which the front retardation (Re) of the optically anisotropic layer is 100 to 200 nm, tilted by + 40 ° with respect to the normal direction of the layer plane, with the in-plane slow axis as the tilt axis (rotation axis) The transfer material according to [17], wherein the retardation values measured by making light having a wavelength λ nm incident are substantially equal.
[24] The method for producing an optical element according to any one of [1] to [5], comprising a step of transferring at least the optically anisotropic layer from the transfer material according to any one of [17] to [23].
[25] The method for producing a transflective liquid crystal display device according to any one of [6] to [16], comprising a step of transferring at least the optically anisotropic layer from the transfer material according to any one of [17] to [23]. .

  According to the present invention, it is possible to provide a transflective liquid crystal display device that can be easily manufactured with a small number of steps and has good display characteristics, and a method for manufacturing the same.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, a liquid crystal display device to which the present invention is applied and a manufacturing method thereof will be described in detail with reference to the drawings.
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 this specification, the Re retardation value is calculated based on the following. Re (λ) represents in-plane retardation and retardation in the thickness direction at the wavelength λ. Re (λ) is measured by the parallel Nicol method, in which light having a wavelength of λ nm is incident in the normal direction of the optically anisotropic layer. 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%. Furthermore, Re is not substantially 0 means that 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.

FIG. 1 is a schematic sectional view of a transflective liquid crystal display device according to an embodiment of the present invention.
The transflective liquid crystal display device shown in FIG. 1 has two transparent substrates (121) facing each other and a liquid crystal layer (131) made of a liquid crystal material sandwiched between the two transparent substrates (121). . On one opposing surface of the transparent substrate (121), a reflective plate (135) formed of a highly reflective material using aluminum, silver, or the like is disposed and covered with a transparent conductive film such as ITO. The transparent electrode (125) which consists of, and the alignment film (126) are formed. Further, on the surface on the opposite side of the substrate (121), a polarizing plate (136) and an optically anisotropic layer that compensates for residual retardation of the liquid crystal layer have a predetermined in-plane retardation (for example, 38 nm). A degree) A-plate (a retardation plate having an optical axis in the plane) is arranged as a compensation plate (132). Hereafter, this side is the back side. Further, on the opposing surface of the opposing transparent substrate (121), a color filter layer (123) of R, G and B colors, a black matrix (122), and a λ / 4 layer at a position corresponding to the reflection region. A retardation layer (124: optically anisotropic layer) is disposed, and an electrode (125) and an alignment film (126) are disposed thereon. A polarizing plate (133) is disposed on the surface opposite to the facing surface of the substrate. Hereinafter, this surface is the front side.

  Each of the R, G, B color pixel areas includes a reflection area (128) on which a reflection plate (135) is formed, and a transmission area (127), and a retardation layer (124) that is a λ / 4 layer. Is formed only in the reflective region (128) and not in the transmissive region (127). That is, the retardation layer (124) is patterned according to the shape of the reflective region.

  The two polarizing plates (133, 136) are arranged with their transmission axes orthogonal. The slow axis direction of the λ / 4 layer retardation layer (124) and the compensation plate (132) is a predetermined angle (here, 45 °, 135 °) with respect to the transmission axis of the polarizing plate (133, 136). ). A liquid crystal layer (131) is sandwiched between two opposing transparent substrates (121). In FIG. 1, the liquid crystal layer is an ECB mode (electrolytic birefringence mode electrically controlled birefringence) in which the slow axis forms an angle of 45 ° with respect to the transmission axis of the polarizing plate. In addition, the alignment directions of the liquid crystal molecules in the liquid crystal layer in the transmission region (127) and the reflection region (128) are the same. The in-plane retardation of the liquid crystal layer is preferably λ / 2 of 275 nm in the transmission region and λ / 4 of 137.5 nm in the reflection region.

The liquid crystal layer can be in the TN mode used in the transmissive liquid crystal display element. In this case, high contrast can be obtained during transmissive display. Furthermore, it is possible to use an IPS mode, a VA mode having excellent viewing angle characteristics, and an OCB mode having excellent response speed.
In this case, the compensation layer (132) is a uniaxial or biaxial optically anisotropic layer (referred to as a-plate) having an extraordinary optical axis in the in-plane direction, or the extraordinary optical axis is a surface. It is desirable to select an optimal layer from an optically anisotropic layer (referred to as c-plate) in a direction perpendicular to.

When the liquid crystal mode is the ECB mode, the λ / 4 layer is preferably a positive uniaxial A-Plate. The same applies when the liquid crystal mode is TN. In the case of TN, those formed by hybrid alignment of discotic liquid crystalline compounds are more desirable.
In addition, when the liquid crystal mode is VA, it is preferable to use a negative C-plate, a complex of the A-Plate, or a biaxial A-Plate. In the case of the IPS mode, a biaxial A-Plate or A positive C-plate is desirable.

The basic principle when an image is actually displayed on the above-described transflective liquid crystal display device shown in FIG. 1 will be described with reference to FIG. For simplicity, the description of the color filter layer and the compensation layer is omitted.
First, the case of white display will be described.
The voltage application to the liquid crystal layer is set to a threshold value or less. At this time, in the reflection part, ambient light incident from the front side is first linearly polarized light by the polarizing plate, and right-handed circularly polarized light by the λ / 4 layer in the reflection region. Since the liquid crystal layer has a phase difference of λ / 4, it is converted again into linearly polarized light and reaches the reflector. The linearly polarized light reflected by the reflecting plate passes through the liquid crystal layer again to become circularly polarized light having the same rotational direction, passes through the λ / 4 layer, becomes linearly polarized light having the same vibration direction as the incident light, and passes through the polarizing plate. Since the incident light is reflected and comes out, the display of this portion is white (or bright).
In the transmission part, the light emitted from the back surface of the substrate by the backlight becomes linearly polarized light that matches the transmission axis of the polarizing plate. When this linearly polarized light enters the liquid crystal layer, since the retardation is λ / 2, the vibration direction is inclined by 90 ° to become linearly polarized light parallel to the transmission axis of the polarizing plate on the front side, and passes through this.

Next, a case where dark display is performed will be described.
A sufficient voltage is applied to the liquid crystal layer to make the retardation viewed from the front almost zero so that the liquid crystal molecules are perpendicular to the substrate surface.
In the reflection portion, ambient light incident from the front side is first converted into linearly polarized light by the polarizing plate, and then is rotated clockwise by the λ / 4 layer in the reflective region. Since the retardation of the liquid crystal layer is almost zero, the light reaches the reflector and is reflected while maintaining its polarization state. At this time, the direction of rotation of the polarized light is reversed, and when the light passes through the liquid crystal layer and passes through the λ / 4 layer again, it is converted into linearly polarized light orthogonal to the transmission axis of the polarizing plate and cannot be transmitted, resulting in black display. In the transmissive portion, light incident from the back side becomes linearly polarized light that matches the transmission axis of the polarizing plate. This linearly polarized light reaches the polarizing plate on the front side as it is, but cannot be transmitted because it is perpendicular to the transmission axis, resulting in black display.

  In the above description, a configuration has been described in which black is displayed when a voltage is applied and white is displayed when no voltage is applied, but the transmission axes of the polarizing plates (133, 136) are set to be parallel and vice versa. Any configuration may be used.

  In this embodiment, a λ / 4 layer (124) having reverse wavelength dispersion characteristics is formed in the reflection region, and a compensation layer is provided on the back side to compensate the residual retardation of the transmission part and improve the contrast. Yes. That is, since there is no fear of color shift due to wavelength dispersion of the λ / 4 layer at the reflection portion, the λ / 2 layer is unnecessary.

  In the first place, the main cause of the hue change is the retardation wavelength dispersion characteristic of an optically anisotropic substance such as a retardation plate. The wavelength dispersion characteristic of retardation is usually such that the retardation becomes smaller as the wavelength becomes longer. For example, in a transflective liquid crystal display device, the λ / 4 plate has a function of converting linearly polarized light and circularly polarized light. When a wavelength G (550 nm) having a retardation of λ / 4 of 137.5 nm is used, it is smaller for the wavelength R (600 nm) and conversely for the wavelength B (450 nm). It gets bigger. In the present invention, in order to solve this problem, Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm) is satisfied, that is, in the visible light region, the phase difference has a reverse dispersion characteristic with respect to the wavelength ( An optically anisotropic layer having a property that the phase difference increases as the wavelength becomes longer is used as a λ / 4 plate or the like.

In the above description, the aspect in which the optically anisotropic layer is used as a λ / 4 plate has been mainly described. However, in the optically anisotropic layer in the present invention, Re is substantially 0 when the phase difference is measured. There is no particular limitation as long as it has at least one incident direction, that is, optical characteristics that are not isotropic. From the viewpoint of easy control of the optical properties used in the liquid crystal cell, it is desirable that the liquid crystal layer containing at least one liquid crystalline compound is cured by irradiating with ultraviolet rays.
The thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, and 0.3 to 10 μm. Is even more preferable.

In order to solve the above-mentioned problem, the present inventor has also searched for an optically anisotropic material having reverse wavelength dispersion characteristics, and intensively studied an optimal structure and manufacturing method. An optically anisotropic layer satisfying the above characteristics can be easily produced by using a predetermined compound described later.
Further, the optical element and transflective liquid crystal display device of the present invention having an optically anisotropic layer patterned into an arbitrary shape can be subjected to pattern exposure and development processes after transferring the optically anisotropic layer from a transfer material. A method of forming; a method of forming a pattern by ejecting a fluid expressing a desired optical anisotropy to a predetermined region by an ink jet method; and applying and drying a fluid expressing a desired optical anisotropy on a predetermined substrate After the liquid crystal phase is formed, it can be manufactured through a pattern exposure and development process.

In the present invention, “patterned into an arbitrary shape” means that at least a region where an optically anisotropic layer is formed and a region where it is not formed are regularly or irregularly arranged on one surface. For example, as described in the above embodiment, in the transflective liquid crystal display device, an optically anisotropic layer formed only on the reflective portion, an optically anisotropic layer formed only on the RGB pixel region, Various aspects are mentioned.
Further, in the present invention, a non-patterned uniform optically anisotropic layer having reverse wavelength dispersion characteristics is separated from an optically anisotropic layer having reverse dispersion characteristics patterned into an arbitrary shape, for example, a liquid crystal cell. You may have in the back side inside or outside the liquid crystal cell.

[Formation of optically anisotropic layer by transfer method]
First, an embodiment in which an optically anisotropic layer having an inverse wavelength dispersion characteristic satisfying the above functions and patterned into an arbitrary shape is formed using a transfer material will be described.
[Transfer material]
As an example of the manufacturing method of the liquid crystal display device of the present invention, there is a method including forming the optically anisotropic layer by transferring it from a transfer material. By forming an optically anisotropic layer using a transfer material, the number of steps can be reduced, and a liquid crystal display device with good display characteristics can be manufactured by a simple method. Here, the transfer material has a support, at least one optically anisotropic layer, and at least one photosensitive resin layer, and the optically anisotropic layer and the photosensitive resin layer are separated from each other. A material used to transfer onto a substrate. FIG. 3 shows schematic sectional views of several examples of the transfer material of the present invention. The transfer material of the present invention shown in FIG. 3A has an optically anisotropic layer 12 and a photosensitive resin layer 13 on a transparent or opaque temporary support 11. The transfer material may have other layers. For example, as shown in FIG. 3 (b), unevenness on the counterpart substrate side is formed between the support 11 and the optically anisotropic layer 12 during transfer. It may have a layer 14 for controlling mechanical characteristics such as cushioning properties for absorbing or providing unevenness followability, and also in the optically anisotropic layer 12 as shown in FIG. A layer 15 that functions as an alignment layer for controlling the alignment of the liquid crystal molecules may be disposed, or both layers may be provided as shown in FIG. Further, as shown in FIG. 3 (e), a peelable protective layer 16 may be provided on the outermost surface for the purpose of protecting the surface of the photosensitive resin layer.

[Support]
The support used for the transfer material in the present invention may be transparent or opaque and is not particularly limited. Examples of the polymer constituting the support include cellulose ester (eg, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate), polyolefin (eg, norbornene-based polymer), poly (Meth) acrylic acid ester (eg, polymethyl methacrylate), polycarbonate, polyester and polysulfone, and norbornene-based polymer are included. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and cellulose ester and norbornene are preferred from the viewpoint of low birefringence. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. Inexpensive polycarbonate, polyethylene terephthalate, and the like are also preferably used.

[Optically Anisotropic Layer Consisting of Composition Containing Liquid Crystalline Compound]
The optically anisotropic layer functions as an optically anisotropic layer that compensates the viewing angle of the liquid crystal display device by being incorporated in the liquid crystal cell as described above. Optically required for optical compensation in combination with other layers (for example, an optically anisotropic layer disposed outside the liquid crystal cell) as well as an aspect in which the optically anisotropic layer alone has sufficient optical compensation capability Embodiments satisfying the characteristics are also included in the scope of the present invention. In addition, the optically anisotropic layer of the transfer material does not need to satisfy the optical characteristics sufficient for the optical compensation capability. For example, the optical anisotropic layer can be optically transmitted through an exposure process performed in the process of being transferred onto the liquid crystal cell substrate. The characteristic may be expressed or changed, and finally the optical characteristic necessary for optical compensation may be exhibited.

  The optically anisotropic layer is preferably formed from a composition containing at least one liquid crystalline compound. 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 the present invention, 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.

The liquid crystal compound usually does not have Δn wavelength dispersion represented by the following formula (0).
Formula (0): Δn (450 nm) / Δn (550 nm) <1.0
In order to develop the wavelength dispersion of Δn that satisfies the equation (0), it is necessary to adjust at least two types of absorption wavelengths and the direction of transition moment. Since Δn is a value obtained by subtracting the refractive index of ordinary light from the refractive index of extraordinary light, the wavelength dispersion of ordinary light is lower than the wavelength dispersion of the refractive index of extraordinary light. (The slope of Δn when the left is on the short wavelength side), the subtracted value satisfies the equation (0). The wavelength dispersion of the refractive index is closely related to the absorption of the substance as represented by the Lorentz-Lorenz equation. Therefore, in order to make the wavelength dispersion of ordinary light more downward, the normal light direction If the absorption wavelength of can be made longer, a molecule satisfying the formula (0) can be designed.

The direction of ordinary light is, for example, the width direction of molecules in a rod-like liquid crystal, and it is very difficult to lengthen the absorption transition wavelength in the width direction of such molecules. In order to lengthen the absorption transition, it is usually possible to widen the π-conjugated system. However, if such a method is used, the width of the molecule is widened, and the liquid crystallinity is It will disappear.
In order to prevent such a decrease in liquid crystallinity, William N. It is possible to use a skeleton in which two rod-like liquid crystals reported by Thurms et al. (Liquid Crystals, 25, 149, 1998) are connected in the lateral direction. Since this skeleton connects two rod-shaped liquid crystals with an ethynyl group, the π-conjugated system of the benzene ring constituting the rod-shaped liquid crystal is conjugated with the π bond of the ethynyl group (tolan skeleton), so the liquid crystallinity is not impaired. In addition, the absorption wavelength in the width direction of the molecule can be lengthened. However, since this Tran skeleton is inclined only about 60 ° with respect to the major axis direction (optical axis direction) of the molecule, in other words, the absorption transition direction is inclined only about 60 °, Not only the absorption wavelength but also the absorption wavelength in the extraordinary light direction is lengthened, and as a result, hardly contributes to wavelength dispersion.

In order to make only the wavelength dispersion of ordinary light more downward, the absorption transition direction is preferably 70 to 90 °, more preferably 80 to 90 with respect to the major axis direction (optical axis direction) of the molecule. It turned out that it needs to be tilted. The closer the tilt angle is to 90 °, the more the absorption in the extraordinary light direction is eliminated. Therefore, it is preferable that only the wavelength dispersion of ordinary light can be lowered.
As described above, the absorption transition mainly contributing to the refractive index of ordinary light has a longer wavelength than the absorption transition mainly contributing to the refractive index of extraordinary light, and the absorption mainly contributing to ordinary light. Molecules whose transition direction is inclined by 70 to 90 ° with respect to the major axis direction (optical axis direction) of the molecule are preferred. In order for the transition direction of absorption mainly contributing to ordinary light to tilt 70 to 90 ° with respect to the long axis direction (optical axis direction) of the molecule, a 6-membered ring and an odd-membered ring (3-membered ring, 5-membered ring, It has been found that a 7-membered ring, a 9-membered ring, etc.) preferably has a condensed partial structure.

  Specifically, a liquid crystal compound represented by the following general formula (I) or a general formula (II) described later can be given. These liquid crystalline compounds may be contained in the optically anisotropic layer as additives as a monomolecular structure, and when these liquid crystalline compounds have a polymerizable group, from these liquid crystalline compounds You may contain in the said optically anisotropic layer in the state of the polymer | macromolecule which has a repeating unit induced | guided | derived.

Formula (I)

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group. A ¹ and A ² each independently represents a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and —CO—. R ¹ , R ² , and R ³ each independently represent a substituent. X is 14th
Represents a non-metallic atom of Group -16 (however, a hydrogen atom or a substituent may be bonded to X). n represents an integer of 0 to 2.

  In particular, a liquid crystal compound represented by the following general formula (I ′) is preferable.

Formula (I ')

In general formula (I ′), L ¹ and L ² each independently represents a single bond or a divalent linking group. A ¹ and A ² each independently represents a group selected from the group consisting of —O—, —NR— (R represents a hydrogen atom or a substituent), —S—, and —CO—. R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represents a substituent. n represents an integer of 0 to 2.

In the general formula (I) or (I ′), the divalent linking group represented by L ¹ and L ² preferably includes the following examples.

  More preferred are -O-, -COO-, and -OCO-.

In general formula (I) or (I ′), R ¹ is a substituent, and when a plurality of R ¹ are present, they may be the same or different and may form a ring. The following can be applied as examples of the substituent.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert- Butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl) Group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octan-3-yl group),

An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, That is, it is a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed, for example, a 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group), a bicycloalkenyl group (substituted or substituted). An unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group), alkini Group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, aromatic A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably Or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy. Group),

A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group or tert-butyldimethylsilyloxy group), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms) Ring oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon number 6-30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably , Substituted or non-substituted with 1 to 30 carbon atoms Carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyl An oxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group. Group), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn- Hexadecyl oxy phenoxycarbonyl group),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylaminocarbonyl Mino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino Group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Amino groups such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylamino Sulfonylamino groups), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonyl An amino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group, a mercapto group, and an alkylthio group (preferably a substituent having 1 to 30 carbon atoms) Or an unsubstituted alkylthio group such as a methylthio group Ethylthio group, n-hexadecylthio group), arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), heterocyclic thio A group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms substituted or An unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group), an alkyl and an arylsulfonyl group ( Preferably, the substitution having 1 to 30 carbon atoms or An unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group),

An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group or a pivaloylbenzoyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl Group (preferred Is a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- ( Methylsulfonyl) carbamoyl group),

Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferably carbon A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinylamino group such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as , Trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group).

  Among the above substituents, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

R ¹ is preferably a halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group, amino group, more preferably A halogen atom, an alkyl group, a cyano group, and an alkoxy group.

R ² and R ³ each independently represents a substituent. An example of R ¹ is given as an example. Preferred are a substituted or unsubstituted benzene ring and a substituted or unsubstituted cyclohexane ring. More preferred are a benzene ring having a substituent and a cyclohexane ring having a substituent, and more preferred are a benzene ring having a substituent at the 4-position and a cyclohexane ring having a substituent at the 4-position.

R ⁴ and R ⁵ each independently represents a substituent. An example of R ¹ is given as an example. Preferably, the Hammett substituent constant σp value is preferably an electron-withdrawing substituent greater than 0, and more preferably has an electron-withdrawing substituent having a σp value of 0 to 1.5. . Examples of such a substituent include a trifluoromethyl group, a cyano group, a carbonyl group, and a nitro group. R4 and R5 may be bonded to form a ring.
As for Hammett's substituent constants σp and σm, for example, Naoki Inamoto, “Hammett's rule-structure and reactivity-” (Maruzen), edited by the Chemical Society of Japan, “New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds V” 2605 (Maruzen), Tadao Nakatani "Theoretical Organic Chemistry" page 217 (Tokyo Kagaku Dojin), Chemical Review, 91, 165-195 (1991).

A ¹ and A ² each independently represent a group selected from the group consisting of —O—, —NR— (wherein R is a hydrogen atom or a substituent), —S—, and —CO—. Preferred are —O—, —NR— (R represents a substituent, and examples of R ¹ are given as examples) or —S—.

X represents a nonmetallic atom belonging to Groups 14-16. However, a hydrogen atom or a substituent may be bonded to X. X is preferably ═O, ═S, ═NR, ═C (R) R (wherein R represents a substituent, and examples of R ¹ are given as examples).
n represents an integer of 0 to 2, preferably 0 or 1.

When the compound represented by the general formula (I) or (I ′) has a polymerizable group, it is preferable because the optical characteristics of the optically anisotropic layer are not changed by heat or the like. As a polymeric group, it is the same as that of illustration of the substituent Q which the compound represented with general formula (III) mentioned later has. The compound represented by the general formula (I) or (I ') may, for example, may have a polymerizable group as a substituent for R ² and / or R ^3.

  Specific examples of the compound represented by the general formula (I) or (I ′) are shown below, but the present invention is not limited to the following specific examples. Regarding the following compounds, unless otherwise specified, the number in parentheses () indicates the exemplified compound (X).

  The synthesis of the compound represented by the general formula (I) or (I ′) can be performed with reference to known methods. For example, exemplary compound (1) can be synthesized according to the following scheme.

In the above scheme, the synthesis from compound (1-A) to compound (1-D) is described in “Journal of Chemical Crystallography” (1997); 27 (9); p. 515-526. It can be performed with reference to the method described in 1.
Further, as shown in the above scheme, methanesulfonic acid chloride was added to a tetrahydrofuran solution of the compound (1-E), N, N-diisopropylethylamine was added dropwise and stirred, and then N, N-diisopropylethylamine was added. Exemplary solution (1) can be obtained by adding dropwise a tetrahydrofuran solution of compound (1-D) and then adding a tetrahydrofuran solution of N, N-dimethylaminopyridine (DMAP).

  For the formation of the optically anisotropic layer, it is also preferable to use a compound represented by the following general formula (II).

式中、ＭＧ¹及びＭＧ²はそれぞれ独立に、２〜８個の環状基から構成される液晶相の発現を誘起する液晶コア部であり、液晶コア部を構成する環状基としては、芳香族環、脂肪族環、及び複素環のいずれでもよく；ＭＧ¹及びＭＧ²を構成する環状基の１つは、Ｌ¹¹及びＬ¹²で置換され；Ｒ¹¹、Ｒ¹²、Ｒ¹³、及びＲ¹⁴はそれぞれ液晶コア部の分子長軸方向に置換している液晶相の発現を誘起する柔軟性のある置換基、双極子作用基及び水素結合性基であり；Ｌ¹¹及びＬ¹²はそれぞれ独立に、液晶コア部ＭＧ¹及びＭＧ²に置換する連結基であり、下記式（ＩＩ）−ＬＡ又は式（ＩＩ）−ＬＢで表され； Formula (II)

In the formula, MG ¹ and MG ² are each independently a liquid crystal core part that induces the expression of a liquid crystal phase composed of 2 to 8 cyclic groups, and the cyclic group constituting the liquid crystal core part is an aromatic group Any of a ring, an aliphatic ring, and a heterocyclic ring; ^one of the cyclic groups constituting MG ¹ and MG ² is substituted with L ¹¹ and L ¹² ; R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ Are flexible substituents, dipole action groups, and hydrogen bonding groups that induce the expression of the liquid crystal phase substituted in the molecular long axis direction of the liquid crystal core; L ¹¹ and L ¹² are each independently , A linking group substituted on the liquid crystal core parts MG ¹ and MG ² , represented by the following formula (II) -LA or formula (II) -LB;

Formula (II) -LA

式中、＊はＭＧ¹を構成する環状基に置換する位置を表し；＃はＰ¹と連結する位置を表し；Ａ¹¹、Ａ¹³及びＡ¹⁴はそれぞれ独立に、―Ｏ−、−ＮＨ−、−Ｓ−、−ＣＨ₂−、−ＣＯ−、−ＳＯ−、又は−ＳＯ₂−を表し；Ａ¹²は−ＣＨ＝又は−Ｎ＝を表し；Ｌ¹¹及びＬ¹²の双方が式（ＩＩ）−ＬＡで表される基の場合、置換基Ｐ¹は単結合、又は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、１，４−フェニレン及びそれらの組み合わせからなる群より選ばれる二価の連結基を表し；Ｌ¹¹及びＬ¹²の一方が、式（ＩＩ）−ＬＢで表される基で、他方が式（ＩＩ）−ＬＡで表される基の場合、置換基Ｐ¹は、＊＝ＣＨ−Ｐ¹¹−＃、又は＊＝Ｎ−Ｐ¹¹−＃で表され（＊は式（ＩＩ）−ＬＢで表される基との連結位置を表し、＃は式（ＩＩ）−ＬＡで表される基との連結位置を表す）；Ｐ¹¹は単結合、又は−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、１，４−フェニレン及びこの組み合わせから選ばれる二価の連結基を表し；Ｌ¹¹及びＬ¹²の双方が式（ＩＩ）−ＬＢで表される基の場合、置換基Ｐ¹は、二重結合、＝ＣＨ−Ｐ¹¹−ＣＨ＝、＝Ｎ−Ｐ¹¹−ＣＨ＝、＝Ｎ−Ｐ¹¹−Ｎ＝を表し；Ｐ¹¹は上記Ｐ¹¹と同義である。 Formula (II) -LB

In the formula, * represents a position substituted with the cyclic group constituting MG ¹ ; # represents a position linked to P ¹ ; A ¹¹ , A ¹³ and A ¹⁴ are each independently —O—, —NH—. , -S-, -CH _2- , -CO-, -SO-, or -SO _2- ; A ¹² represents -CH = or -N =; both L ¹¹ and L ¹² are represented by the formula (II ) In the case of a group represented by -LA, the substituent P ¹ is a single bond or a divalent group selected from the group consisting of -CH = CH-, -C≡C-, 1,4-phenylene and combinations thereof. In the case where one of L ¹¹ and L ¹² is a group represented by the formula (II) -LB and the other is a group represented by the formula (II) -LA, the substituent P ¹ is represented by * = CH-P ¹¹ - #, or * = N-P ¹¹ - represented by # (* represents a linking position between the groups of the formula (II) -LB, # in formula (II) -LA Group represented Represents the coupling position); P ¹¹ is a single bond, or a -CH = CH -, - C≡C-, represents a 1,4-phenylene and a divalent linking group selected from the combination; L ¹¹ and L ¹² Are both groups represented by the formula (II) -LB, the substituent P ¹ is a double bond, ═CH—P ¹¹ —CH═, ═N—P ¹¹ —CH═, ═N—P ^11. -N =; P ¹¹ has the same meaning as P ¹¹ above.

  The compounds represented by the general formula (I) are described in detail in [2005] to [0083] of JP-A-2005-289980, and the exemplified compounds are also described in [0085] to [0098] of the same publication. Can be used.

Along with the compound represented by the general formula (I) or (II), a rod-like or discotic liquid crystalline compound having forward wavelength dispersion characteristics may be used for forming the optically anisotropic layer.
Examples of rod-like liquid crystalline compounds having forward wavelength dispersion characteristics include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and 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.

Formula (VI): Q ⁶¹ -L ⁶¹ -A ⁶¹ -L ⁶³ -ML ⁶⁴ -A ⁶² -L ⁶² -Q ⁶²
Wherein each Q ⁶¹ and Q ⁶² are each independently a reactive group, the L ^61, L ^62, L ⁶³ and L ⁶⁴ each represent a single bond or a divalent linking group, L ⁶³ and At least one of L ⁶⁴ is preferably —O—CO—O—. A ⁶¹ and A ⁶² 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 (VI) will be described in more detail. In the formula, Q ⁶¹ and Q ⁶² 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 ⁶¹ , L ⁶² , L ⁶³ and L ⁶⁴ include —O—, —S—, —CO—, —NR ⁶² —, —CO—O—, —O—CO. —O—, —CO—NR ⁶² —, —NR ⁶² —CO—, —O—CO—, —O—CO—NR ⁶² —, —NR ⁶² —CO—O—, and NR ⁶² —CO—NR ⁶² A divalent linking group selected from the group consisting of-is preferred. R ⁶² is an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. In this case, at least one of L ⁶³ and L ⁶⁴ is —O—CO—O— (carbonate group). In the formula (VI), Q ⁶¹ -L ⁶¹ and Q ⁶² -L ⁶² -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 ⁶¹ and A ⁶² represent spacer groups having 2 to 20 carbon atoms. An alkylene group having 2 to 12 carbon atoms, an alkenylene group, and an alkynylene group are 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 (VII) is preferable.
Formula (VII): - (- W 61 -L 65) n -W 62 -
In the formula, each of W ⁶¹ and W ⁶² independently represents a divalent cyclic alkylene group or cyclic alkenylene group, a divalent aryl group or a divalent heterocyclic group, and L ⁶⁵ represents a single bond or a linking group. Specific examples of the linking group include specific examples of groups represented by L ^{61 to} L ⁶⁴ in the formula (VI), —CH ₂ —O—, and —O—CH ₂ —. n represents 1, 2 or 3.

W ⁶¹ and W ⁶² include 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 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 mesogen group represented by the general formula (VII) are shown below. These may be substituted with the above substituents.

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

  Another embodiment of the liquid crystalline compound having forward wavelength dispersion characteristics is a discotic liquid crystalline compound. The optically anisotropic layer may be 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 reaction with heat, light, etc., to have a high molecular weight and lose liquid crystallinity.

It is preferable to use a discotic liquid crystalline compound represented by the following general formula (VIII).
Formula (VIII): 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 (VIII), 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 contains a compound (for example, a coating solution) containing the compound represented by the general formula (I) or (II) and, if desired, another liquid crystal compound on the surface of the alignment layer described later. It is preferably a layer prepared by coating and making the alignment state exhibiting a desired liquid crystal phase, and then fixing the alignment state by irradiation with heat or ionizing radiation. When a rod-like liquid crystal compound having a reactive group is used as the liquid crystal compound, polarized light is applied to the cholesteric alignment or the twisted hybrid cholesteric alignment while the inclination angle gradually changes in the thickness direction in order to develop biaxiality. It is necessary to distort by. 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).

When the optically anisotropic layer is uniaxial, it is possible to accurately optically compensate a VA mode, IPS mode or transflective mode liquid crystal cell by optimizing the optical anisotropy of the upper or lower polarizing plate protective film. Therefore, it is preferable. In any case, for the improvement of the color viewing angle characteristics, the retardation wavelength dispersion of the polarizing plate protective film is general, that is, the retardation becomes smaller as the wavelength becomes longer, so that a wider wavelength for the liquid crystal cell. Optical compensation can be made accurately over a wide range.
The optically anisotropic layer may be prepared by aligning the compound represented by the general formula (I) or (II) so that the directors of the liquid crystal are aligned in one direction. Such alignment is realized by a method of aligning a non-chiral liquid crystal layer on a rubbing alignment layer or photo-alignment layer, a method of aligning by a magnetic field or an electric field, a method of aligning by applying an external force such as stretching or shearing, etc. it can.

  The liquid crystalline compound represented by the general formula (I) or (II) may be fixed in any orientation state of horizontal orientation, vertical orientation, tilt orientation, and twist orientation in the layer. Orientation, vertical orientation, and twist orientation are preferred, and horizontal orientation is most preferred. The horizontal alignment is not required to be strictly parallel, and in this specification, it means an alignment having an inclination angle of less than 10 degrees with the horizontal plane.

  When two or more optically anisotropic layers made of a liquid crystalline compound are laminated, the combination of the liquid crystalline compounds is not particularly limited, and the layers are all formed using the liquid crystalline compound represented by the general formula (I). A laminate of layers formed using a liquid crystalline compound represented by the general formula (II), a compound of the general formula (I) and a compound of the general formula (II), respectively. Any of the laminates of the formed layers may be used. In addition, it may be a laminate of a layer formed using a discotic liquid crystalline compound and / or a layer formed using 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.

  The optically anisotropic layer is preferably formed by applying a coating liquid containing a liquid crystalline compound and the following polymerization initiator and other additives onto a predetermined alignment layer described later. 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 compounds]
The aligned liquid crystalline compound is preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystal compound. 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, U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,221,970).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, more preferably 0.5 to 5% by mass, based on the solid content of the coating solution. 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.

By containing at least one of the compounds 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 specification, “horizontal 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 parallel, and in the case of a disc-like liquid crystal, the circle of the core of the disc-like liquid crystal compound. The horizontal plane of the board and the transparent support is said to be parallel, but it is not required to be strictly parallel. In the present specification, an orientation with an inclination angle of less than 10 degrees with the horizontal plane is meant. And 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.

式中、Ｒ¹、Ｒ²及びＲ³は各々独立して、水素原子又は置換基を表し、Ｘ¹、Ｘ²及びＸ³は単結合又は二価の連結基を表す。Ｒ¹〜Ｒ³で各々表される置換基としては、好ましくは置換もしくは無置換の、アルキル基（中でも、無置換のアルキル基又はフッ素置換アルキル基がより好ましい）、アリール基（中でもフッ素置換アルキル基を有するアリール基が好ましい）、置換もしくは無置換のアミノ基、アルコキシ基、アルキルチオ基、ハロゲン原子である。Ｘ¹、Ｘ²及びＸ³で各々表される二価の連結基は、アルキレン基、アルケニレン基、二価の芳香族基、二価のヘテロ環残基、−ＣＯ−、―ＮＲ^a−（Ｒ^aは炭素原子数が１〜５のアルキル基又は水素原子）、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−及びそれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。二価の連結基は、アルキレン基、フェニレン基、−ＣＯ−、−ＮＲ^a−、−Ｏ−、−Ｓ−及び−ＳＯ₂−からなる群より選ばれる二価の連結基又は該群より選ばれる基を少なくとも二つ組み合わせた二価の連結基であることがより好ましい。アルキレン基の炭素原子数は、１〜１２であることが好ましい。アルケニレン基の炭素原子数は、２〜１２であることが好ましい。二価の芳香族基の炭素原子数は、６〜１０であることが好ましい。 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, the compounds described in paragraph numbers [0092] to [0096] of JP-A-2005-99248 can be used, and the synthesis method of these compounds is also described in the specification. ing.

  The amount of the compound represented by 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. 02-1 mass% is especially preferable. In addition, the compounds represented by the general formulas (1) to (3) may be used alone or in combination of two or more.

[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 an undercoat 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 rubbing treatment layer 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. The alignment layer may have a function as an oxygen blocking film.

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

Moreover, as a vapor deposition material for the inorganic oblique vapor deposition film, SiO ₂ is representative, metal oxides such as TiO ₂ and ZnO ₂ , fluorides such as MgF ₂ , and metals such as Au and Al. . 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.

  The optically anisotropic layer can be transferred by aligning the liquid crystalline compound on the temporary alignment layer, fixing the alignment, and then using an adhesive on the transparent support, but from the viewpoint of productivity. Is preferably formed directly without transfer.

[Photosensitive resin layer]
The photosensitive resin layer used for the transfer material in the present invention is made of a photosensitive resin composition, and when exposed to light through a mask or the like, a difference in transferability to the substrate occurs between the exposed and unexposed areas. There is no particular limitation as long as it is positive or negative. The photosensitive resin layer is preferably formed from a resin composition containing at least (1) an alkali-soluble resin, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or a photopolymerization initiator system. . In addition, in the embodiment in which the optically anisotropic layer is formed simultaneously with the color filter on the substrate, (4) it is preferably formed from a colored resin composition containing a colorant such as a dye or pigment.
Hereinafter, the components (1) to (4) will be described.

(1) Alkali-soluble resin The alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. 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-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, 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 And a multi-component copolymer. The binder polymer having these polar groups may be used alone or in the form of a composition used in combination with a normal film-forming polymer, and the content relative to the total solid content of the colored resin composition 20-50 mass% is common, and 25-45 mass% is preferable.

(2) Monomer or oligomer The monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by light irradiation. . 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.

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is used. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 The listed 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.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

(4) 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 dye or pigment include pigments described in paragraph No. [0033] of JP-A No. 2004-302015 and column 14 of US Pat. No. 6,790,568.

  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. The pigment red 254 is preferably 80% by mass or more, particularly preferably 90% by mass or more. C. I. The pigment green 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. C. I. Pigment Blue 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass 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 the 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 photosensitive resin 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 difference in contrast between the colored pixels is within 600 because the amount of light leakage from each colored pixel portion during black display does not differ greatly, and the color balance of black display is good.

  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 contrast measurement is the same as the polarizing plate used for the liquid crystal display device using the color filter.

  In a color filter formed of a photosensitive resin 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. 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, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ 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). C _m F _{2m + 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 C _m F _{2m + 1} is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, based on the monomer (a). R ₁ represents a hydrogen atom or a methyl group. Moreover, n shows 1-18, and 2-10 are preferable especially. R ² and R ³ shown in the general formula (b) each independently represent a hydrogen atom or a methyl group, and R ⁴ 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 contains the monomer represented by the general formula (a) and the general formula (b), and the weight ratio of the general formula (a) / the general formula (b) is 20/80 to 60/40. It is characterized by containing a coalescence. 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 photosensitive resin layer, and 0.1-7 mass% is especially preferable. The surfactant contains a predetermined amount of a surfactant having a specific structure, an ethylene oxide group, and a polypropylene oxide group, and a liquid crystal provided with the photosensitive resin layer by containing it in a specific range in the photosensitive resin layer. Display unevenness of the 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 the above-mentioned particularly preferable surfactant is contained in the photosensitive resin layer to produce a color filter, it is preferable in that display unevenness is improved.

  Specific examples of preferable fluorine-based surfactants include compounds described in paragraph numbers [0054] to [0063] of JP-A No. 2004-163610. 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. In the present invention, a compound described in paragraphs [0046] to [0052] of JP-A No. 2004-331812, which is a fluorine-based surfactant not containing the monomer represented by the general formula (a), is used. Is also preferable.

[Other layers]
It is preferable to form a thermoplastic resin layer between the support and the optically anisotropic layer of the transfer material in order to control the mechanical properties and the unevenness followability. As the component used for the thermoplastic resin layer, organic polymer materials described in JP-A-5-72724 are preferable. It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

  In the transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity. The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  The thermoplastic resin layer and the intermediate layer can also be used as the alignment layer. In particular, polyvinyl alcohol and polyvinyl pyrrolidone preferably used for the intermediate layer are also effective as an alignment layer, and it is preferable that the intermediate layer and the alignment layer are made into one layer.

  A thin protective film is preferably provided on the resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the resin layer. As the protective film material, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.

  The optically anisotropic layer and the photosensitive resin layer, and the orientation layer, the thermoplastic resin layer, and the intermediate layer, which are formed as required, are dip coat method, air knife coat method, curtain coat method, roller coat method, wire bar. It can be formed by coating by a coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

[Method of forming optically anisotropic layer using transfer material]
The method for transferring the transfer material on the substrate in the present invention is not particularly limited, and the method is not particularly limited as long as the optically anisotropic layer and the photosensitive resin layer can be simultaneously transferred onto the substrate. For example, the transfer material referred to in the present invention formed in a film shape is attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the photosensitive resin layer side facing the substrate surface side. be able to. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. Thereafter, the support may be peeled off, and another layer such as an electrode layer may be formed on the surface of the optically anisotropic layer exposed by peeling.

  The substrate that is the transfer material for transferring the transfer material is, for example, a transparent substrate, a soda glass plate having a silicon oxide film on the surface, a low expansion glass, a non-alkali glass, a known glass plate such as a quartz glass plate, Or a plastic film etc. can be mentioned. The material to be transferred may be one in which a layer such as a solid optically anisotropic layer is provided on a transparent support. Moreover, the material to be transferred can be well adhered to the photosensitive resin layer by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

In order to form the λ / 4 layer in the reflective region, pattern exposure is performed after the transfer. In pattern exposure, a predetermined mask may be arranged above the photosensitive resin layer formed on the transfer material, and then exposed from above the mask through the mask, or using a laser or an electron beam. Exposure may be performed with focus on a predetermined position without a mask. By development, a pattern in which a laminate of a specific resin layer and an optically anisotropic layer is arranged on a substrate at a predetermined position is formed. In the case of a transflective liquid crystal display device, a substrate having a λ / 4 layer in the reflective region can be obtained by performing this process using a mask having a shape corresponding to the reflective region. Here, as the light source for exposure, any light source capable of irradiating light in a wavelength region capable of curing the resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

Moreover, there is no restriction | limiting in particular as a developing solution used for the image development process after exposure, Well-known developing solutions, such as the thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developer preferably has a resin-type developing behavior such as a resin layer. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable, but is further miscible with water. A small amount of an organic solvent having Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and 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. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

  As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used. By spraying a developer onto the exposed resin layer with a shower, the uncured portion can be removed. In addition, it is preferable to spray an alkaline solution having a low solubility of the resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. As the cleaning liquid, known ones can be used (including phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Film Co., Ltd.)”) or carbonic acid. Sodium / phenoxyoxyethylene surfactant-containing, trade name “T-SD2 (manufactured by FUJIFILM Corporation)”) is preferable. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

[Formation of optically anisotropic layer by inkjet method]
Next, an embodiment in which an optically anisotropic layer having an inverse wavelength dispersion characteristic and patterned in an arbitrary shape only in a reflective region is formed using an ink jet will be described.
In the present embodiment, a fluid such as a solution exhibiting a predetermined optical anisotropy is ejected using an ink jet apparatus, and the fluid is discharged into the fine region (for example, on the R pixel, the G pixel, and the B pixel). Forming a layer. The fluid preferably contains at least one kind of liquid crystal compound, and particularly preferably contains at least one compound represented by the general formula (I) or the general formula (II). Those prepared so as to form a liquid crystal phase after drying are preferred. 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.

Also in this embodiment, the optically anisotropic layer may be formed on the alignment film. That is, an alignment film may be formed in advance, and the fluid may be discharged to a fine region of the alignment film. The alignment film that can be used in this embodiment is the same as the alignment film that can be used in the embodiment of the transfer method. A method for forming the alignment film is not particularly limited, but in the present embodiment, it is preferable to form the alignment film by an ink jet method as in the formation of the optically anisotropic layer.
After the ejection of the fluid is completed, the fluid layer is optionally dried to form a liquid crystal phase and cured by exposure to form an optically anisotropic layer. In order to form a liquid crystal phase, it may be heated as desired, and in that case, a heating device may be used.

  The fluid is preferably curable, that is, a fluid prepared from the curable composition as a fluid such as a solution. As the polymerization initiator and the like to be contained in the curable composition, various polymerization initiators described in the embodiment of the transfer method can be used. The fluid may contain an additive such as an orientation control agent, and these examples are the same as the various additives described in the embodiments of the transfer method. Also, examples of the solvent used for the preparation of the fluid are the same as the examples of the solvent that can be used for the preparation of the coating liquid in the embodiment of the transfer method.

  There are no particular restrictions on the ejection conditions of the ink or the like when forming the optically anisotropic layer, but when the viscosity of the fluid for forming the optically anisotropic layer is high, it may be at room temperature or under heating (for example, 20 to 70 ° C. ), It is preferable from the viewpoint of injection stability that the ink is ejected at a reduced viscosity. It is preferable to keep the temperature of the ink or the like as constant as possible because the viscosity fluctuation of the ink or the like greatly affects the droplet size and the droplet ejection speed as it is and causes image quality degradation.

  The ink jet head used in the above method (hereinafter also simply referred to as a head) is not particularly limited, and various known ones can be used. A continuous type and a 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 of the fluid is 5 to 25 mPa · s, and to control the fluid temperature so that the fluctuation range of the viscosity is within ± 5%. Further, the drive frequency is preferably 1 to 500 kHz.

[Formation of optically anisotropic layer by development method]
Next, an embodiment in which the optically anisotropic layer having the above reverse wavelength dispersion characteristic is formed using a development method, that is, coating, exposure, and development steps will be described.
In the present embodiment, a fluid such as a solution exhibiting a predetermined optical anisotropy is applied to the surface and dried as desired to obtain a liquid crystal phase. The fluid such as the liquid solution preferably contains at least one kind of liquid crystal compound, and in particular, contains at least one compound represented by the general formula (I) or the general formula (II). Is preferred. Those prepared so as to form a liquid crystal phase after drying are preferred. After forming into a liquid crystal phase, an optically anisotropic layer patterned into a predetermined shape can be formed by imagewise exposure, curing the exposed portion or solubilizing and developing the exposed portion.

  The fluid is preferably a positive or negative photosensitive composition prepared as a fluid such as a solution so that development is possible. Therefore, the fluid is, together with the liquid crystalline compound, a photosensitive material, for example, a material that can be used for producing a photosensitive resin layer of a transfer material used in the embodiment of the transfer method, specifically, (1 ) Alkali-soluble resin, (2) monomer or oligomer, and (3) photopolymerization initiator or photopolymerization initiator may be contained. These preferred examples are as described above.

  The fluid may contain an additive such as an alignment control agent, and these examples are the same as the examples of various additives described in the embodiment of the transfer method. Also, examples of the solvent used for the preparation of the fluid are the same as the examples of the solvent that can be used for the preparation of the coating liquid in the embodiment of the transfer method.

The fluid can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method).
The fluid is applied to the surface by the above method and then dried as desired to form a liquid crystal phase. In order to form a liquid crystal phase, it may be heated as desired, and in that case, a heating device may be used. Also in this embodiment, the fluid may be applied onto the alignment film, and a liquid crystal phase may be formed using the alignment control ability of the alignment film. The alignment film that can be used in this embodiment is the same as the alignment film that can be used in the embodiment of the transfer method.

  After the liquid crystal phase is formed, it is exposed imagewise. Imagewise exposure can be performed, for example, using a photomask. Thereafter, the exposed portion or the unexposed portion is removed by development to obtain an optically anisotropic layer having a predetermined shape. As for the development method, a method of removing an unexposed portion with an aqueous solution or an organic solvent, or an unexposed portion is heated to an isotropic phase transition temperature or higher of the liquid crystal to eliminate anisotropy, and then uncured. It is preferable to use a method of forming an isotropic phase by polymerizing a polymerizable liquid crystal and curing it.

  The optical element of the present invention is characterized by having an optically anisotropic layer having the above-mentioned reverse dispersion characteristics, which is patterned into a predetermined shape. Examples of the optical element of the present invention include various examples such as a color filter substrate having the optically anisotropic layer on the substrate and a liquid crystal cell substrate.

The present invention includes a layer containing a compound represented by the above general formula (I) or (II) patterned into a predetermined shape, or a compound represented by the following general formula (I) or (II): The present invention also relates to a transflective liquid crystal display device having an optically anisotropic layer containing a polymer containing a derived repeating unit. The transflective liquid crystal display device of the present invention may have the following other constituent members.
[Other components]
The liquid crystal display device of the present invention may further include a reflective region including a reflective layer, a transmissive region, a color filter layer, and a viewing angle compensation layer. The reflective region including the reflective layer, the transmissive region, the color filter layer, and the viewing angle compensation layer of the liquid crystal display device can be formed by various conventionally known methods. The color filter layer or the viewing angle compensation layer may also be formed using a transfer material. Further, in the production of color filters, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by overlapping colored resin compositions that form a color filter, and a transparent electrode is formed thereon. It is preferable from the viewpoint of cost reduction that the spacers are formed by overlapping the protrusions for split orientation as necessary. Further, the viewing angle compensation layer is formed by aligning a polymerizable composition containing the rod-like liquid crystalline compound represented by the general formula (VI) or the discotic liquid crystalline compound represented by the general formula (VIII) with an alignment film. It is preferable to form the film by applying it on the surface of the resin and the like, aligning the liquid crystalline molecules, and then fixing the alignment state by polymerization. Specific examples of the materials used in the polymerizable composition, the immobilization method, the preparation of the coating solution, and the alignment film are the same as the materials and methods used when forming the optically anisotropic layer of the transfer material of the present invention. It is.

  Specific examples of the method for manufacturing the liquid crystal display device of the present invention will be described below. The materials, reagents, substance amounts and ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the following specific examples.

<Example 1>
(Preparation of coating liquid CU-1 for thermoplastic resin layer)
The following composition was prepared and filtered through a polypropylene filter having a pore size of 30 μm, and used as a coating liquid CU-1 for alignment layer.
────────────────────────────────── ――――――
Coating liquid composition for thermoplastic resin layer (%)
────────────────────────────────── ――――――
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, weight average molecular weight = 100,000, Tg≈70 ° C.)
5.89
Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.)
13.74
BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.20
Megafuck F-780-F (manufactured by Dainippon Ink & Chemicals, Inc.) 0.55
Methanol 11.22
Propylene glycol monomethyl ether acetate 6.43
Methyl ethyl ketone 52.97
────────────────────────────────── ――――――

(Preparation of coating liquid AL-1 for intermediate layer / alignment layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as the intermediate layer / alignment layer coating solution AL-1.
──────────────────────────────────――
Coating solution composition for intermediate layer / 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 AL-2 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. As the modified polyvinyl alcohol, one described in JP-A-9-152509 was used.
───────────────────────────────────
Coating liquid composition for alignment layer (mass%)
─────────────────────────────────――
Modified polyvinyl alcohol AL-1-1 4.01
Water 72.89
Methanol 22.83
Glutaraldehyde (crosslinking agent) 0.20
Citric acid 0.008
Citric acid monoethyl ester 0.029
Citric acid diethyl ester 0.027
Citric acid triethyl ester 0.006
───────────────────────────────────

(Preparation of coating liquid LC-X for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 1 μm and used as a coating liquid LC-X for an optically anisotropic layer.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
LC-X-1 19.16
Photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.57
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.19
LC-X-2 0.08
Chloroform 80.0
──────────────────────────────────――

(Preparation of coating liquid LC-1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 1 μm and used as a coating liquid LC-1 for an optically anisotropic layer.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan 30.00
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.90
Methyl ethyl ketone 68.00
──────────────────────────────────――
The horizontal alignment agent (LC-1-1) was obtained from Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002). The photopolymerization initiator (LC-1-2) was synthesized by the method described in EP1388538A1, page 21.

(Preparation of coating liquid LC-2 for optical compensation layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 1 μm to prepare an optical compensation layer coating liquid LC-2.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Exemplary Compound TE-8 (R: 8, m = 4) 32.43
Description of discotic compound Ethylene glycol-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 3.60
Cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 0.72
Photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.08
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.36
Methyl ethyl ketone 61.81
──────────────────────────────────――

(Preparation of coating liquid PP-1 for photosensitive resin layer)
After preparing the following composition, it filtered with the polypropylene filter with the hole diameter of 0.2 micrometer, and used as coating liquid PP-1 for photosensitive resin layers.
──────────────────────────────────――
Composition of coating liquid PP-1 for photosensitive resin layer (mass%)
──────────────────────────────────――
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio (weight average molecular weight 37,000) 5.0
Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio (weight average molecular weight 40,000) 2.45
KAYARAD DPHA (Nippon Kayaku Co., Ltd.) 3.2
Radical polymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) 0.75
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.25
Propylene glycol monomethyl ether acetate 27.0
Methyl ethyl ketone 53.0
Cyclohexanone 9.2
Megafuck F-176PF (Dainippon Ink Chemical Co., Ltd.) 0.05
──────────────────────────────────――

(Preparation of coating solution PP-K1 for photosensitive resin layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating solution PP-K1 for the photosensitive resin layer. In the adjustment method, first, K pigment dispersion and propylene glycol monomethyl ether acetate were weighed, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 1, Hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine, MegaFac F-176PF And added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).
──────────────────────────────────――
Composition for coating liquid PP-K1 for photosensitive resin layer (mass%)
──────────────────────────────────――
K pigment dispersion 25.0
Propylene glycol monomethyl ether acetate (PGMEA) 8.0
Methyl ethyl ketone 53.494
Binder 1 9.1
DPHA solution 4.2
2,4-Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-promophenyl] -s-triazine 0.160
Hydroquinone monomethyl ether 0.002
Megafuck F-176PF (Dainippon Ink Co., Ltd.) 0.044
──────────────────────────────────――

The compositions in the above table are as follows.
[K pigment dispersion composition]
──────────────────────────────────――
K pigment dispersion composition (%)
──────────────────────────────────――
Carbon black (Degussa, Special Black 250)
13.1
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone
0.65
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio (weight average molecular weight 37,000) 6.72
Propylene glycol monomethyl ether acetate 79.53
──────────────────────────────────――

──────────────────────────────────――
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
──────────────────────────────────――

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

(Preparation of photosensitive resin transfer material for black matrix)
On the roll-shaped polyethylene terephthalate film temporary support body of thickness 75micrometer, the coating liquid CU-1 for thermoplastic resin layers was apply | coated and dried using the slit-shaped nozzle. Next, the intermediate layer / alignment layer coating solution AL-1 was applied and dried. Furthermore, the photosensitive resin composition PP-K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.3 μm was provided, and a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded. In this way, a photosensitive resin transfer material K-1 for black matrix in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

[Example 1]
(Production of photosensitive resin transfer material)
On a polyethylene terephthalate roll film temporary support having a thickness of 75 μm, the coating liquid CU-1 for thermoplastic resin layer was applied and dried using a slit nozzle. Next, the alignment layer coating liquid AL-1 was applied and dried. The film thickness of the thermoplastic resin layer was 14.6 μm, and the alignment layer was 1.6 μm. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-X for optically anisotropic layer was applied thereon with a # 5.5 wire bar coater, and a plane irradiation type far-infrared heater (16φ, long After heating and aging at 125 ° C. for 3 minutes while irradiating at 500 mm, 0.7 kW), a layer having a uniform liquid crystal phase is formed, and then a 160 W / cm air-cooled metal halide lamp (eye graphics Co., Ltd.) The optically anisotropic layer was fixed by irradiating ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 400 mJ / cm ² to form an optically anisotropic layer having a thickness of 1.9 μm.
Finally, the photosensitive resin composition PP-1 was applied and dried to form a photosensitive resin layer having a thickness of 0.7 μm, thereby preparing a photosensitive resin transfer material RET-1.

[Reference Example 1]
(Production of photosensitive resin transfer material)
On a polyethylene terephthalate roll film temporary support having a thickness of 75 μm, the coating liquid CU-1 for thermoplastic resin layer was applied and dried using a slit nozzle. Next, the alignment layer coating liquid AL-1 was applied and dried. The film thickness of the thermoplastic resin layer was 14.6 μm, and the alignment layer was 1.6 μm. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-1 for optically anisotropic layer is applied thereon with a # 3 wire bar coater, and the film surface temperature is 95 ° C. for 2 minutes by heating and aging. And a layer having a uniform liquid crystal phase was formed. Further, immediately after aging, this layer was irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 400 mJ / cm ² using a 160 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) under air. Then, the optically anisotropic layer was fixed to form an optically anisotropic layer having a thickness of 0.9 μm. Finally, the photosensitive resin composition PP-1 was applied and dried to form a 1.7 μm photosensitive resin layer, thereby producing a photosensitive resin transfer material RET-2.

(Phase difference measurement)
Each of the transfer material prepared in Example 1 and Reference Example 1, was transferred to a transparent glass substrate, after removing the film temporary support was irradiated with ultraviolet rays of 400 mJ / cm ^2, air at 200 ° C. in an oven Bake treatment was performed for 1 hour in the atmosphere. The film was allowed to cool to room temperature to prepare a retardation plate. The front retardation Re at an arbitrary wavelength λ was measured by a parallel Nicol method using a fiber spectrometer. Retardations of 650 nm, 550 nm, and 450 nm were measured as wavelengths λ corresponding to R, G, and B, respectively. The phase difference measurement results are shown in the following table.

  The optically anisotropic layer formed from the transfer material of Example 1 satisfies Re (450) <Re (550) <Re (659), and is a λ / 4 plate for each wavelength. Was confirmed.

[Example 2: Inkjet method]
The rod-like liquid crystal used for the preparation of the coating liquid LC-1 for optically anisotropic layer of Example 1 was changed to the rod-like liquid crystal of the exemplary compound (110), and the same procedure was repeated except that methyl ethyl ketone was changed to chloroform. A coating liquid LC-2 for anisotropic layer was prepared.

(Preparation of optically anisotropic layer)
The alignment layer coating liquid AL-1 was applied to a glass substrate and dried. The alignment layer was 1.6 μm. Subsequently, the formed alignment layer was rubbed, and then the optically anisotropic layer coating liquid LC-2 was deposited thereon using a piezo-type head, followed by heat drying and ripening at 140 ° C. for 2 minutes to be uniform. A layer having a liquid crystal phase was formed. 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. Thus, an optically anisotropic layer I-2 having a thickness of 2.9 μm was formed. It was confirmed that the formed optically anisotropic layer was formed as a fine pattern.

[Reference Example 2]
The same except that the rod-like liquid crystal used for the preparation of the coating liquid LC-1 for optically anisotropic layer was changed to the rod-like liquid crystal represented by the following formula (provided that x = 4) described in JP-A-2006-64858. Coating liquid LC-3 was prepared in the same manner as in Example 2 to form optically anisotropic layer I-3. It was confirmed that the formed optically anisotropic layer was formed as a fine pattern.

(Δn measurement)
The optical anisotropy of the prepared optically anisotropic layer is obtained by measuring the dependency of Re on the light incident angle using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.). Δn was determined from the measured film thickness. The results of Δn measurement are shown in the following table.

[Example 3: Development method]
On the glass substrate, the alignment layer coating liquid AL-1 was applied and dried using a slit nozzle. The alignment layer was 1.6 μm. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-2 for optically anisotropic layer is applied thereon with a # 5.5 wire bar coater, and heated and aged for 2 minutes at 140 ° C. to be uniform. A layer having a liquid crystal phase was formed. Further, immediately after aging, this layer was irradiated with UV light (illuminance 200 mW / cm ² , irradiation amount 1000 mJ / cm ² ) through a photomask in a nitrogen atmosphere with an oxygen concentration of 0.3% or less, It was immersed in an acetone solution, and the liquid crystal film in the unexposed part was removed.
It was confirmed that the formed optically anisotropic layer was formed as a fine pattern.

[Example 4]
(Production of transflective LCD 1)
In Example 4, a full-color panel having the same optical configuration as that of the liquid crystal display device 1 shown in FIG. 1 was produced.
First, a transflective color filter 1 was produced by the following method.
-Formation of black (K) image-
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
After peeling off the protective film of the photosensitive resin transfer material K-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries (Lamic II type)), a rubber roller temperature of 130 ° C. Lamination was performed at a linear pressure of 100 N / cm and a conveyance speed of 0.4 m / min.
After peeling off the protective film, with the proximity type exposure machine (UXH-1000SM manufactured by USHIO ELECTRIC CO., LTD.) Having an ultra-high pressure mercury lamp, the substrate and mask (quartz exposure mask with image pattern) are set and the exposure mask The distance between the pattern surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² .
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Film Co., Ltd.), 30 Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Subsequently, sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T- Using CD1, manufactured by Fuji Film Co., Ltd., shower development was performed at a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterned pixel.
Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name: T-SD1, manufactured by Fuji Film Co., Ltd.), a cone type nozzle pressure of 0.02 MPa Residue removal was performed with a rotating brush having nylon bristles to obtain a black (K) image. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp from the resin layer side, and then heat treated at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Formation of Red (R) Green (G) Blue (B) Pixels-
FUJIFILM RESEARCH & DEVELOPMENT No. 44 (1999), page 25, using the transer system (manufactured by FUJIFILM Corporation), R, G, B color filters on the portion corresponding to the RGB pixel portion on the substrate on which the black matrix is formed A layer was formed. The thickness of each color layer was 1.8 μm.

-Formation of optically anisotropic layer in reflective region-
Next, the transfer material RET-1 produced in Example 1 is transferred onto the substrate in the same process as the photosensitive resin transfer material K-1, and the portion corresponding to the reflective region is irradiated with UV light. The photomask designed as described above was placed with a proximity exposure machine at a distance of 100 μm from the surface of the photosensitive resin layer, and was exposed with an irradiation energy of 100 mJ / cm ² through the photomask with an ultrahigh pressure mercury lamp. Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Film Co., Ltd.), 30 Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Subsequently, sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T- Using CD1, manufactured by Fuji Film Co., Ltd., shower development was performed at a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterned pixel. Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name: T-SD1, manufactured by Fuji Film Co., Ltd.), a cone type nozzle pressure of 0.02 MPa Residue removal was performed with a rotating brush having nylon bristles to obtain an image of the reflection area. Thereafter, the substrate was further post-exposed with 500 mJ / cm ² of light from the resin layer side with an ultrahigh pressure mercury lamp. This substrate was baked at 220 ° C. for 50 minutes to obtain the target substrate.

(Formation of transparent electrode)
On the color filter 1 and the λ / 4 layer produced above, an ITO transparent electrode film having a thickness of 1000 mm was formed by vacuum sputtering.
Film formation: After vacuuming to about 10 ^-5 Pa in a vacuum chamber, the substrate is heated to 240 degrees with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ^-1 Pa, and ITO is blown off from the target surface. , Deposited to a thickness of 1000 Å.
Photolithograph: A photoresist (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was uniformly coated to a thickness of 2 μm by spin coating. After pre-baking in a 100 ° C. baking oven, a pattern was baked using a photomask having a desired pattern in an exposure apparatus. The exposure amount and the exposure time were determined by appropriately selecting the optimum equipment conditions. The exposed substrate was developed with a developer (containing tetramethylammonium hydroxide: manufactured by Tokyo Ohka Kogyo Co., Ltd.) and post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, etching is performed while spraying an ITO etchant (containing ferric chloride: manufactured by Kanto Chemical Co., Ltd.) with a swinging shower head, confirming that the ITO film has been sufficiently dissolved, and then removing the etchant with a pure water shower. Washed off and dried with a high-pressure air knife using dry air. Next, the resist was peeled off. While spraying a resist stripping solution (containing 2-aminoethanol and NMP: manufactured by Tokyo Ohka Kogyo Co., Ltd.) with a shower head, the resist was stripped by applying a roll brush. The stripping solution was swept away with a hot water shower and an air knife.

(Formation of alignment layer)
Further, a polyimide alignment film was provided thereon. The alignment material used was polyimide SR1254 made by JSR, and was applied to the region where the pixel electrodes were arranged by roll coating. After coating, prebaking was performed in an atmosphere at 80 ° C. for 15 minutes, and baking was further performed at 200 ° C. for 60 minutes. As a result, an alignment layer having a thickness of about 0.5 μm was obtained. This alignment film was subjected to alignment treatment by a rubbing apparatus. The rubbing cloth was cotton, the rotation speed was 500 rpm, and the indentation depth was 0.3 mm.

(Opposite substrate)
A glass substrate having substantially the same material and size as the color filter substrate was prepared.

(Reflection pattern formation)
Washing:
While pure water adjusted to 25 ° C. was sprayed with a shower, it was washed with a rotating brush having nylon bristles, and dried with an air knife using dry air.
Film formation:
This was performed with a vacuum sputtering film forming apparatus. After evacuating to about 10 ^-4 Pa in a vacuum chamber, the substrate is heated to 200 degrees with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ^-1 Pa, and AL is blown off from the target surface. Deposited to thickness.
Photolithograph:
A photoresist (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was uniformly coated to a thickness of 2 μm by spin coating. After pre-baking in a 100 ° C. baking oven, a pattern was baked using a photomask having a desired pattern in an exposure apparatus. The exposed substrate was developed with a developer (containing tetramethylammonium hydroxide: manufactured by Tokyo Ohka Kogyo Co., Ltd.) and post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, perform etching while spraying with an AL etching solution (containing phosphoric acid: manufactured by Kanto Chemical) with a swinging shower head, confirm that the film has dissolved completely, wash off the etching solution with a pure water shower, and dry air. The water was dried with a high-pressure air knife using, and dried. Next, the resist was peeled off. While spraying a resist stripping solution (containing 2-aminoethanol and NMP: manufactured by Tokyo Ohka Kogyo Co., Ltd.) with a shower head, the resist was stripped by applying a roll brush. The stripping solution was swept away with a hot water shower and an air knife.
By the above method, as shown in FIG. 1, a reflective layer was formed only at a position on the opposite substrate facing the position where the λ / 4 layer was formed.

(Formation of transparent electrode)
An ITO transparent conductive film was formed by vacuum sputtering on the surface of the substrate on which the reflective layer was formed. After evacuating to about 10 ^-5 Pa in a vacuum chamber, the substrate is heated to 200 degrees with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ^-1 Pa, and ITO is blown off from the target surface. Deposited to thickness.

(Preparation of photosensitive transfer material for protrusions)
A thermoplastic resin layer coating solution CU-1 was applied on a 75 μm thick polyethylene terephthalate film temporary support and dried to provide a thermoplastic resin layer having a dry film thickness of 15 μm.
Next, the intermediate layer / alignment layer coating solution AL-1 was applied on the thermoplastic resin layer and dried to provide an intermediate layer having a dry film thickness of 1.6 μm.
On the said intermediate | middle layer, the coating liquid which consists of the following prescription was apply | coated and dried, and the photosensitive resin layer for liquid crystal orientation control protrusions with a dry film thickness of 2.5 micrometers was provided.
────────────────────────────────────────Protrusion coating composition (%)
───────────────────────────────────────────────────────────────────────────────────────── 53.3)
Methyl ethyl ketone 46.66
Mega Fuck F-176PF 0.04
────────────────────────────────────────
Further, a 12 μm-thick polypropylene film is attached to the surface of the photosensitive resin layer as a cover film, and a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a cover film are laminated in this order on the temporary support. A transfer material was prepared.

(Forming protrusions)
The cover film is peeled off from the projection transfer material produced above, and the surface of the photosensitive resin layer and the surface of the counter substrate on which the transparent electrode film is provided are overlaid, and a laminator (manufactured by Hitachi Industries, Ltd.) (Lamic II type)) was used for bonding under conditions of a linear pressure of 100 N / cm, a temperature of 130 ° C., and a conveying speed of 2.2 m / min. Thereafter, only the temporary support of the transfer material was peeled and removed at the interface with the thermoplastic resin layer. In this state, the photosensitive resin layer, the intermediate layer, and the thermoplastic resin layer are laminated in this order on the color filter side substrate.
Next, a proximity exposure machine is disposed above the outermost thermoplastic resin layer so that the photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and an ultrahigh pressure mercury lamp is passed through the photomask. Proximity exposure was performed at an irradiation energy of 70 mJ / cm ² . Thereafter, a 1% triethanolamine aqueous solution was sprayed onto the substrate at 30 ° C. for 30 seconds with a shower type developing device to dissolve and remove the thermoplastic resin layer and the intermediate layer. At this stage, the photosensitive resin layer was not substantially developed.
Subsequently, 0.085 mol / L sodium carbonate, 0.085 mol / L sodium hydrogen carbonate, and 1% sodium dibutylnaphthalenesulfonate aqueous solution were developed while spraying on the substrate at 33 ° C. for 30 seconds using a shower type developing device. Then, unnecessary portions (uncured portions) of the photosensitive resin layer were developed and removed. Then, a protrusion made of a photosensitive resin layer patterned into a desired shape was formed on the color filter side substrate. Next, the color filter side substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes, so that liquid crystal alignment control protrusions having a height of 2.5 μm and a vertical cross-sectional shape are formed on the color filter side substrate. Could be formed.

(Formation of facing side alignment layer)
A polyimide alignment layer was formed on the transparent conductive layer in the same manner as the color filter substrate. The alignment material used was polyimide SR1254 made by JSR, and was selectively applied to the region where the pixel electrode was arranged by a roll coating method. After coating, prebaking was performed in an atmosphere at 80 ° C. for 15 minutes, and baking was further performed at 200 ° C. for 60 minutes. As a result, an alignment layer having a thickness of about 0.5 μm was obtained. This alignment film was subjected to alignment treatment by a rubbing apparatus. The rubbing cloth was made of cotton, a rotation speed of 500 rpm, and an indentation depth of 0.3 mm. The rubbing direction was set to be an anti-parallel direction with respect to the orientation direction of the color filter substrate.

(Seal pattern formation)
A seal pattern was formed around the counter substrate. An epoxy resin containing 1.0 wt% of a seal spacer with a particle diameter of 6.8 μm (Strectbond XN-21S manufactured by Nissan Chemical Industries) is opened with a seal dispenser device in a predetermined area surrounding the display area corresponding to the liquid crystal injection port. I printed it in the form. This was calcined at 80 ° C. for 30 minutes.

(Overlapping)
The color filter substrate 1 and the counter substrate were adjusted so as to overlap at a correct position. In this state, while applying a pressure of 0.03 MPa, the bonded glass substrate was heat-treated at 180 ° C. for 60 minutes to cure the sealing agent, thereby obtaining a laminate of two glass substrates. A balloon type device was used for firing.

(Liquid crystal injection)
A liquid crystal material was injected into the glass substrate laminate using a liquid crystal injection device. In the rod-like nematic liquid crystal of the liquid crystal material refractive index anisotropy 0.55, placed in a liquid crystal dish, and degassed and held 60 minutes under a vacuum of 10 ^-1 Pa with a vacuum chamber together with the substrate stack. After sufficiently evacuating the vacuum, the portion of the inlet provided in the seal was immersed in the liquid crystal and then returned to atmospheric pressure and held for 180 minutes to fill the gap between the glass substrates with the liquid crystal. Thereafter, the substrate laminate was taken out from the injection apparatus, and a UV curable epoxy adhesive was applied to the injection port portion and cured to obtain a liquid crystal cell.

(Polarizing plate pasting)
On the back side of the liquid crystal cell, a uniaxial retardation film having a retardation of 38 nm is attached as a residual retardation compensation film in a direction in which the slow axis is orthogonal to the alignment direction of the liquid crystal, A liquid crystal panel was obtained by pasting polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. in an arrangement in which the polarizing plate absorption axis was orthogonal to the alignment direction of the liquid crystal.
(Transmission part retardation measurement)
Retardation in the transmission region of the liquid crystal cell was measured with a Otsuka Electronics optical material inspection device (RETS-100) to measure retardation in a state in which no voltage was applied.

(Example 5: Production of transflective LCD 2)
In Example 5, as an optical compensator for the transmission part, a disc-shaped liquid crystalline compound was hybrid-aligned on the support, and an optical compensator for the transmission part obtained by polymerizing this was produced. Arranged. In this embodiment, an effect that the optical characteristics of the transmission part are excellent can be expected.
(Preparation of optical compensator for transmission part)
《One-sided saponification treatment of cellulose ester film》
A commercially available cellulose acetate film Fujitac TD80UF (Fuji Film Co., Ltd., Re = 3 nm, Rth = 50 nm) was passed through a dielectric heating roll at a temperature of 60 ° C., and the film surface temperature was raised to 40 ° C. An alkaline solution having the composition shown below was applied at 14 ml / m ² using a bar coater. Then, after retaining for 10 seconds under a steam far infrared heater (manufactured by Noritake Co., Ltd.) heated to 110 ° C., 3 ml / m ^{2 of} pure water was applied using the same bar coater. The film temperature at this time was 40 degreeC. Next, washing with a fountain coater and draining with an air knife were repeated three times, and then the sample was retained in a drying zone at 70 ° C. for 2 seconds and dried.
─────────────────────────────
Alkaline solution composition
─────────────────────────────
Potassium hydroxide 4.7
Water 14.7
Isopropanol 64.8
Propylene glycol 14.8
Surfactant (SF-1) 1.0
─────────────────────────────

As described above, the alignment layer coating liquid AL-2 is applied to the transparent support that has been saponified on one side with a # 14 wire bar coater, 60 seconds with warm air at 60 ° C., and 150 seconds with warm air at 90 ° C. By drying, an alignment layer having a thickness of 1.0 μm was formed. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-2 for optically anisotropic layer is coated thereon with a # 5 wire bar coater, and heated and dried at 125 ° C. for 3 minutes to be uniform. After forming a layer having a liquid crystal phase, an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ^{2 is} irradiated using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm in the air. Then, the optically anisotropic layer was fixed to form an optically anisotropic layer having a thickness of 3.1 μm, and an optical compensator for the transmission part was produced. It was confirmed that the discotic liquid crystalline compound was fixed in a hybrid alignment state in the optically anisotropic layer.

Formation of black (K) image and color filter having λ / 4 optical anisotropic layer using red (R) green (G) blue (B) pixel and transfer material RET-1 in the same procedure as in Example 4 A substrate was formed.
Further, in the same procedure as in Example 4, formation of a reflection pattern, followed by formation of a transparent electrode, preparation of a photosensitive transfer material for protrusions, formation of protrusions, formation of an opposing side alignment layer, formation of a seal pattern, overlapping Together, liquid crystal injection was performed.

(Formation of transmission part compensation layer)
On the back side of the substrate, the optical compensator for the transmission part was attached, and the pressure-sensitive adhesive was pasted with the optically anisotropic layer facing the substrate surface. At this time, the rubbing direction of the optical compensator and the rubbing direction of the substrate were antiparallel. Further, a polarizing plate HLC2-2518 manufactured by Sanlitz Co., Ltd. was attached to both surfaces of the liquid crystal cell in an arrangement in which the polarizing plate absorption axis was orthogonal to the alignment direction of the liquid crystal to obtain a liquid crystal panel.

(Reference Example 3: Production of comparative transflective LCD)
Also in Reference Example 3, a full-color panel having the same optical configuration as that of the liquid crystal display device shown in FIG. 1 was produced. However, for comparison, a λ / 4 layer was formed using the transfer material prepared in Reference Example 1. Specifically, it was produced by the following method.
Black (K) image formation and red (R) green (G) blue (B) pixel formation were performed in the same manner as in Example 4.
-Formation of optically anisotropic layer in reflective region-
Next, the transfer material RET-2 produced in Reference Example 1 was transferred and formed on the substrate in the same process as the photosensitive resin transfer material K-1. Further, a transparent electrode and an alignment layer were formed in the same manner as in Example 5 to obtain a color filter substrate 2. The counter substrate was produced in the same manner as in Example 5. The counter substrate and the color filter substrate were overlapped and fired in the same manner as in Example 4, and then a liquid crystal material was injected to produce a comparative transflective liquid crystal cell.
(Polarizing plate pasting)
On the back side of the liquid crystal cell, a uniaxial retardation film having a retardation of 38 nm was attached as a residual retardation compensation film in a direction in which the slow axis was orthogonal to the alignment direction of the liquid crystal. Further, polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were pasted on both sides to obtain a comparative transflective liquid crystal panel.
(Transmission part retardation measurement)
When the retardation in the transmission region of this liquid crystal cell was measured in the same manner as in Example 4, it was approximately 267 nm.

(Contrast evaluation of transflective LCD)
Each of the transflective LCDs produced in Examples 4 and 5 and Reference Example 3 was placed in a dark room, and parallel light extracted from a C light source was incident from a direction inclined by 5 ° with respect to the panel surface. The reflected light intensity in white display (voltage 0 V) and black display (voltage 3 V) was measured with a luminance meter (BM5 manufactured by TOPCOM) to obtain a contrast value. Furthermore, the color observation when visually observed from an oblique direction was also observed. The results are shown in the table below.

  In addition, FIG. 4 shows the reflection luminance spectrum in the black display state at this time. It was confirmed that the LCDs of Examples 4 and 5 had less leakage light than the LCD of Reference Example 3.

Further, for the LCDs of Examples 4 and 5, the contrast viewing angle characteristics of the transmissive part were measured.
Each LCD is placed in a dark room, C light source is incident from the back as a backlight, the panel is displayed in white (voltage 0V) and black (voltage 3V), and the transmitted light at each display is viewed angle-contrast characteristics It measured with the measuring apparatus (EZ-Contrast made from ELDIM). FIG. 5 shows the result of the LCD of Example 4, and FIG. 6 shows the result of the LCD of Example 5. It was confirmed that the liquid crystal display device of Example 5 using the transmission part compensation layer using a discotic liquid crystal compound showed better viewing angle contrast characteristics than Example 4.

It is a schematic sectional drawing of an example of the liquid crystal display device of this invention. It is the schematic diagram used in order to demonstrate the principle of operation of the liquid crystal display device of this invention. It is a schematic sectional drawing of some examples of the transfer material of this invention. It is a figure which shows the reflection spectrum at the time of the black display of the transflective liquid crystal display device produced in Example 4, 5 and Reference Example 3. FIG. FIG. 11 is a diagram showing contrast viewing angle characteristics of a transmissive portion of a transflective liquid crystal display device manufactured in Example 4. FIG. 10 is a diagram showing contrast viewing angle characteristics of a transmissive portion of a transflective liquid crystal display device manufactured in Example 5.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Temporary support 12 Optically anisotropic layer 13 Photosensitive resin layer 14 Mechanical property control layer 15 Orientation control layer 16 Protective layer 121 Transparent substrate 122 Black matrix 123 Color filter layer 124 Retardation layer (optically anisotropic layer)
125 Transparent electrode layer 126 Alignment layer 127 Transmission region 128 Reflection region 131 Liquid crystal layer 132 Transmission portion compensation plate 133 Polarizing layer A
135 Reflector 136 Polarizing layer B

Claims (24)

It is patterned into an arbitrary shape, which contains a compound represented by the following general formula (I), or the optically anisotropic layer containing a polymer comprising repeating units derived from a compound represented by the following general formula (I) An optical element comprising:
Formula (I)

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represents a substituent; X represents a non-metallic atom of Groups 14-16 , however, the X may be bonded hydrogen atom or a substituent; n is to table an integer of 0 to 2. The optically anisotropic layer has a phase difference Δnd (450 nm) measured at a wavelength of 450 nm, a phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a phase difference Δnd (650 nm) measured at a wavelength of 650 nm. The optical element according to claim 1, wherein Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm) is satisfied. The optical element according to claim 1, wherein the optically anisotropic layer is a layer transferred from a transfer material. The optically anisotropic layer contains a liquid crystal composition containing at least one compound represented by the general formula (I ) from the ink jet type discharge head to form a liquid crystal phase, and is then exposed to the liquid crystal composition. The optical element according to claim 1, wherein the optical element is a layer formed by curing the composition. By applying a liquid crystal composition containing at least one compound represented by the general formula (I ) to the surface to form a liquid crystal phase, the optically anisotropic layer is subjected to an exposure step and a development step. The optical element according to claim 1, wherein the optical element is a formed layer. A transflective liquid crystal display device having an optically anisotropic layer patterned into an arbitrary shape, wherein the optically anisotropic layer contains a compound represented by the following general formula (I ) , or the following general A transflective liquid crystal display device comprising a polymer containing a repeating unit derived from a compound represented by the formula (I 1 ) :
Formula (I)

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represents a substituent; X represents a non-metallic atom of Groups 14-16 , however, the X may be bonded hydrogen atom or a substituent; n is to table an integer of 0 to 2. The optically anisotropic layer has a phase difference Δnd (450 nm) measured at a wavelength of 450 nm, a phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a phase difference Δnd (650 nm) measured at a wavelength of 650 nm. The transflective liquid crystal display device according to claim 6, wherein Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm) is satisfied. The transflective liquid crystal display device according to claim 6, wherein the optically anisotropic layer is a λ / 4 plate. A pair of transparent substrates and a liquid crystal layer disposed between the pair of substrates, wherein the optically anisotropic layer is provided inside one of the pair of transparent substrates. Item 9. The transflective liquid crystal display device according to any one of Items 6 to 8. 10. The transflective liquid crystal display device according to claim 6, further comprising a reflective region and a transmissive region, wherein the optically anisotropic layer is formed in the reflective region. The transflective liquid crystal display device according to any one of claims 6 to 10, wherein the optically anisotropic layer is uniaxial or biaxial. The optically anisotropic layer is a layer having an optical axis of extraordinary light in an in-plane direction or in a direction perpendicular to the plane. Transflective liquid crystal display device. The transflective liquid crystal display device according to any one of claims 6 to 12 , further comprising at least one viewing angle compensation layer. A surface having a pair of transparent substrates and a liquid crystal layer disposed between the pair of substrates, having a reflective layer on one surface of the pair of transparent substrates, and having the reflective layer of the transparent substrate The transflective liquid crystal display device according to claim 13, wherein the viewing angle compensation layer is provided on a surface opposite to the surface. The transflective type according to claim 13 or 14, wherein the viewing angle compensation layer has a layer formed by polymerizing a polymerizable composition containing a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound. Liquid crystal display device. 16. The transflective liquid crystal display device according to claim 6, wherein the liquid crystal mode is an ECB, TN, IPS, VA, or OCB mode. A support, on the support contains a compound represented by the following general formula (I), or contains a polymer including a repeating unit derived from a compound represented by the following general formula (I) optical A transfer material having an anisotropic layer and at least one photosensitive resin layer:
Formula (I)

In the formula, L ¹ and L ² each independently represent a single bond or a divalent linking group; A ¹ and A ² each independently represent —O— or —NR— (R represents a hydrogen atom or a substituent). ), -S- and -CO-; R ¹ , R ² and R ³ each independently represents a substituent; X represents a non-metallic atom of Groups 14-16 However, a hydrogen atom or a substituent may be bonded to X, and n represents an integer of 0 to 2 . The optically anisotropic layer has a phase difference Δnd (450 nm) measured at a wavelength of 450 nm, a phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a phase difference Δnd (650 nm) measured at a wavelength of 650 nm. The transfer material according to claim 17, wherein Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm) is satisfied. The transfer material according to claim 17 or 18, wherein the optically anisotropic layer is a λ / 4 plate. The transfer material according to claim 17, wherein the optically anisotropic layer is uniaxial or biaxial. The transfer material according to any one of claims 17 to 20, wherein the optically anisotropic layer is a layer having an optical axis of extraordinary light in an in-plane direction or in a direction perpendicular to the surface. The transfer material according to any one of claims 17 to 21, wherein the optically anisotropic layer is a layer having no optical axis. The optically anisotropic layer has a front retardation (Re) of 100 to 200 nm, a wavelength λ nm from a direction inclined + 40 ° with respect to the normal direction of the layer plane with the in-plane slow axis as the tilt axis (rotation axis). The transfer material according to any one of claims 17 to 22, wherein the retardation values measured by making light incident are substantially equal. The production of the transflective liquid crystal display device according to any one of claims 6 to 15, further comprising a step of transferring at least the optically anisotropic layer from the transfer material according to any one of claims 17 to 22. Method.

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