JP2007279705A - Translucent liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a translucent liquid crystal display device which can be made thin and has satisfactory display characteristics. <P>SOLUTION: The translucent liquid crystal display device has at least one layer of optically anisotropic layers 11 and 17 each containing a layer formed by polymerizing a polymerizable composition containing a disk-like liquid crystalline compound or a bar-like liquid crystalline compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a transflective liquid crystal display device having a reflective region and a transmissive region.

  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.

As described above, the 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 the cost and increases the thickness of the cell. There is. Further, since the λ / 4 plate and λ / 2 plate used do not satisfy the performance in the entire visible light range, there is a problem with respect to viewing angle characteristics such as coloring.
Patent Document 3 discloses a retardation film composed of a single polymer alignment film for the purpose of expanding the viewing angle of a transflective liquid crystal display device, and retardation values at wavelengths (λ) of 450 nm, 550 nm, and 650 nm. First optical anisotropic element comprising a retardation film in which Re (λ) satisfies Re (450) <Re (550) <Re (650) and 0.2 ≦ Re (λ) /λ≦0.3 And a second optically anisotropic element, which is a liquid crystal film formed of a liquid crystalline polymer material exhibiting optically positive uniaxiality and in which a nematic hybrid alignment formed in a liquid crystal state is fixed, is a transflective type It has been proposed to be used for a liquid crystal display element.
Patent Document 4 discloses (A) a positive refractive index anisotropy having a thickness of 20 μm or more and 70 μm or less as a laminated retardation film capable of achieving λ / 4 or λ / 2 in a wide wavelength region. A film having an optical axis in the plane of the film, and (B) a layer on one side of the film (A), having a refractive index anisotropy and having an optical axis in the normal direction of the layer surface, and 0 ≦ R (550) ≦ 300 nm, R (λ1) / R (λ2) <1, and 10 ≦ Rth (550) ≦ 400 nm (where R (550) is the in-plane retardation of the film at a wavelength of 550 nm, R (λ1 ), R (λ2) is the in-plane retardation of the film at the respective wavelengths λ1 (nm) and λ2 (nm) (400 nm <λ1 <λ2 <780 nm), and Rth (550) is the layer at the wavelength of 550 nm. Satisfy vertical phase difference value in the plane of Laminated retardation film is proposed that. In the example of Patent Document 4, improvement of viewing angle characteristics is confirmed using such a laminated retardation film in a transflective liquid crystal display device.
JP 2000-29010 A JP 2000-35570 A JP 2004-125830 A JP 2006-284703 A

  In Patent Documents 3 and 4, a stretched polycarbonate film is used to obtain predetermined optical characteristics. However, in order to satisfy the predetermined optical characteristics, the polycarbonate film has a certain thickness (in the order of several tens of μm). is required. On the other hand, there is a demand for further thinning of cellular phones and the like that are used for transflective liquid crystal display devices.

  The present invention solves such problems, and an object of the present invention is to provide a transflective liquid crystal display device that can be thinned and has good display characteristics.

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の整数を表す； Means for solving the above-mentioned problems are as follows.
[1] A compound containing a compound represented by the following general formula (I) or (II) or a polymer containing a repeating unit derived from a compound represented by the following general formula (I) or (II) A transflective liquid crystal display device comprising at least one optically anisotropic layer:

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—, —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 nonmetallic 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；

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 for the liquid crystal core parts MG ¹ and MG ² , represented by the following formula (II) -LA or formula (II) -LB;

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。

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 transflective liquid crystal display device according to [1], further comprising at least one viewing angle compensation layer.
[3] 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 visible light wavelength region. The transflective liquid crystal display device of [1] or [2], wherein the phase difference Δnd (650 nm) satisfies Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm).
[4] The transflective liquid crystal display device according to any one of [1] to [3], wherein the optically anisotropic layer is a λ / 4 plate.
[5] The transflective liquid crystal display device according to any one of [1] to [4], wherein the optically anisotropic layer is uniaxial or biaxial.
[6] Any one of [1] to [5], 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.
[7] 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 The transflective liquid crystal display device according to any one of [1] to [6], wherein the viewing angle compensation layer is provided on a surface opposite to the surface having a surface.
[8] The [1] to [7], 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. Any transflective liquid crystal display device.
[9] The transflective liquid crystal display device according to any one of [1] to [8], wherein the liquid crystal mode is an ECB, TN, IPS, VA, or OCB mode.
[10] The transflective liquid crystal display device according to any one of [1] to [9], wherein the optically anisotropic layer is a layer transferred from a transfer material.

  According to the present invention, it is possible to provide a transflective liquid crystal display device which can be thinned and has good display characteristics.

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.

[Transflective liquid crystal display]
A schematic cross-sectional view of one embodiment of a transflective liquid crystal display device of the present invention is shown in FIG.
The transflective liquid crystal display device shown in FIG. 1 includes a liquid crystal cell LC having two transparent substrates 12 and 16 facing each other and a liquid crystal layer 14 made of a liquid crystal material sandwiched between the two transparent substrates; The optically anisotropic layers 11 and 17 are provided between the pair of polarizing plates 10 and 18 disposed across the LC; and between the liquid crystal cell LC and the polarizing plates 10 and 18, respectively. Although omitted in the drawing, a backlight is disposed on the back surface of the back-side polarizing plate 18. Further, the transflective liquid crystal display device of FIG. 1 has a transmissive region and a reflective region. In the transmissive region, a transmissive electrode 15 a made of a transparent conductive film such as ITO is reflected on the opposite surface of the transparent substrate 16. In the region, a reflective electrode 15b made of a highly reflective material using aluminum, silver, or the like is formed. Further, a counter electrode 13 made of a transparent conductive film such as ITO is formed on the counter surface of the substrate 12 disposed so as to be the same as the transmissive electrode 15a. Although not shown in the drawing, an RGB or RGBW color filter is disposed between the substrate 12 and the counter electrode 13, and between the counter electrode 13 and the liquid crystal layer 14, liquid crystal molecules in the liquid crystal layer 14 are disposed. An alignment layer for controlling the alignment is formed.

  The pair of polarizing plates 10 and 18 are arranged with their transmission axes orthogonal. The transmission axes of the polarizing plates 10 and 18 are set so as to form a predetermined angle with respect to the slow axis of the liquid crystal layer 14 of the liquid crystal cell LC. The preferred angle varies depending on the mode of the liquid crystal cell LC.

  The display mode of the liquid crystal cell LC is not particularly limited, and may be a TN mode used in a transmissive liquid crystal display element. When the liquid crystal cell LC is in the TN mode, high contrast can be obtained during transmissive display. Furthermore, IPS mode, VA mode, and OCB mode liquid crystal cells having excellent viewing angle characteristics can be used.

The optically anisotropic layers 11 and 17 contain a compound represented by a predetermined formula (I) or (II) described later, or are repeatedly derived from a compound represented by the formula (I) or (II) It is a layer containing a polymer containing units.
In the first place, the main cause of the hue change in the transflective liquid crystal display device is the retardation wavelength dispersion characteristic of an optically anisotropic material such as a retardation plate. The wavelength dispersion characteristic of retardation is usually such that the retardation becomes smaller as the wavelength becomes longer. When the wavelength G (550 nm) retardation is 137.5 nm with λ / 4, it is smaller for the wavelength R (600 nm) and conversely for the wavelength B (450 nm). It gets bigger. In order to solve this problem, in this embodiment, the in-plane retardation has reverse wavelength dispersion characteristics (the in-plane retardation has a characteristic that the longer the wavelength, the larger the wavelength with respect to light in the visible light range). Optical anisotropic layers 11 and 17 that function as λ / 4 plates and are formed using a predetermined optical anisotropic material are used.

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.
Further, when the liquid crystal mode is VA, it is desirable to use a negative C-plate or a complex with the A-Plate, and when the liquid crystal mode is IPS mode, the biaxial A-Plate is desirable.

  The optically anisotropic layers 11 and 17 may be integrally formed on the protective films of the polarizing plates 12 and 18. Further, it may be formed on the inner or outer surface of the substrates 12 and 16 of the liquid crystal cell LC. For the formation of the optically anisotropic layers 11 and 17, a transfer material described later is useful.

FIG. 2 shows a schematic cross-sectional view of another embodiment of the transflective liquid crystal display device of the present invention. 2, the same members as those in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted.
The transflective liquid crystal display device of FIG. 2 further includes an optical compensation layer 19 between the polarizing plate 18 and the optically anisotropic layer 17. The optical compensation layer 19 can be selected from retardation films having various performances according to the mode of the liquid crystal display device. For example, in the TN or ECB mode transflective liquid crystal display device, the optical compensation layer 19 is preferably selected from an optically anisotropic layer formed by curing a disc-like liquid crystal composition in a hybrid alignment state. . In the embodiment of the VA mode transflective liquid crystal display device, the optical compensation layer 19 is preferably selected from a negative C-plate.

  The transflective liquid crystal display device of the present invention is not limited to the configuration shown in FIGS. 1 and 2, and the configurations of conventionally known transflective liquid crystal display devices in various modes can be used.

Hereinafter, materials used for production, production methods, and the like of the optically anisotropic layer used in the transflective liquid crystal display device of the present invention will be described in detail.
[Optically anisotropic layer]
The optically anisotropic layer referred to in the present invention is not particularly limited as long as it has at least one incident direction in which Re is not substantially 0 when the phase difference is measured, that is, has optical characteristics that are not isotropic. However, from the viewpoint of easy control of optical characteristics, it is desirable that the liquid crystal layer containing at least one liquid crystal compound is cured by irradiating it with ultraviolet rays.

[Optically Anisotropic Layer Consisting of Composition Containing Liquid Crystalline Compound]
As described above, the optically anisotropic layer functions as an optically anisotropic layer for compensating the viewing angle of the liquid crystal display device. Of course, the optically anisotropic layer alone has a sufficient optical compensation capability, and satisfies the optical characteristics required for optical compensation in combination with other layers (for example, an optical compensation layer or a protective film for a polarizing plate). Embodiments are also included in the scope of the present invention.

  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 formula (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 right is the longer wavelength side, If 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, it is 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 (trans 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. By using the following predetermined compound, in the wavelength region of visible light, the phase difference Δnd (450 nm) measured at a wavelength of 450 nm, the phase difference Δnd (550 nm) measured at a wavelength of 550 nm, and a wavelength of 650 nm were measured. An optically anisotropic layer satisfying Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm) with a phase difference Δnd (650 nm) can be easily formed as a thin layer. 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.

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 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 represents a nonmetal atom of Groups 14 to 16 (provided that 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.

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 represent 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 there are a plurality of R ^{1 s} , 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 , C1-C30 substitution or non-position 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 a 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's “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” 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 properties 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 scheme, the synthesis from the compound (1-A) to the 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；

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 for the liquid crystal core parts MG ¹ and MG ² , represented by the following formula (II) -LA or formula (II) -LB;

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。

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 compound represented by the general formula (II) has detailed descriptions [0026] to [0083] of JP-A-2005-289980, and exemplary compounds thereof are also [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 a forward wavelength dispersion characteristic 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. The rod-like liquid crystalline compound having a low-molecular reactive group that is particularly preferably used is a rod-like liquid crystalline compound represented by the following general formula (VI).

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 a spacer group 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 a 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.

As W ⁶¹ and W ⁶² , 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).

  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. Immobilization

It is preferable to carry 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, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,221,970).

It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is more preferable that it is 0.5-5 mass%. 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 compound represented by the following general formulas (1) to (3) in the composition for forming the optically anisotropic layer, the molecules of the liquid crystalline compound are substantially horizontally aligned. be able to. In the present 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 is used. The horizontal plane of the board and the transparent support is said to be parallel, but it is not required to be strictly parallel, and in this specification, the inclination angle formed by the horizontal plane is less than 10 degrees. 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。

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.

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.

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 paragraphs [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 layer subjected to a rubbing treatment of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, and ω-tricosanoic acid, dioctadecylmethylammonium chloride and stearyl Examples thereof include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field.

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

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

  Although there is no restriction | limiting in particular about the thickness of the said optically anisotropic layer, From a viewpoint of thickness reduction, it is preferable that it is 0.1-20 micrometers, and it is more preferable that it is 0.1-10 micrometers.

  The optically anisotropic layer may be directly formed on the surface of a protective film for a polarizing plate, for example, by a coating method. Moreover, you may form using the transfer material demonstrated below. That is, as an example of the method for producing a transflective 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 transflective liquid crystal display device with good display characteristics can be manufactured by a simple method.

Hereinafter, a transfer material useful for forming the optically anisotropic layer in a liquid crystal display device will be described.
[Transfer material]
The transfer material usable in the present invention contains a support 51 and a compound represented by the general formula (I) or (II) as shown in FIG. 3A, or the general formula (I). Or it has at least the optically anisotropic layer 52 containing the polymer containing the repeating unit induced | guided | derived from the compound represented by (II). As shown in FIG. 3A, it is preferable that at least one photosensitive resin layer 53 is further provided. The photosensitive resin layer is useful because it facilitates transfer of the optically anisotropic layer even when it is not subjected to a process such as patterning. Further, for example, as shown in FIG. 3C, between the support 51 and the optically anisotropic layer 52, mechanical property control such as cushioning for absorbing irregularities on the counterpart substrate side during transfer is performed. Alternatively, it may have a layer 54 for imparting unevenness follow-up, and as shown in FIG. 3 (d), an orientation for controlling the orientation of liquid crystalline molecules in the optically anisotropic layer 52. A layer 55 that functions as a layer may be disposed, or both layers may be provided as shown in FIG. Moreover, as shown in FIG.3 (f), you may provide the protective layer 56 which can peel on the outermost surface for the objectives, such as surface protection 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 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]
The optically anisotropic layer included in the transfer material is the same as the optically anisotropic layer formed in the liquid crystal display device. However, the optically anisotropic layer included in the transfer material does not need to satisfy the optical characteristics sufficient for the optical compensation ability. Then, it may finally exhibit optical characteristics necessary for optical compensation.

[Photosensitive resin layer]
The transfer material preferably has a photosensitive resin layer. The photosensitive resin layer is made of a photosensitive resin composition, and the photosensitive resin layer includes at least (1) an alkali-soluble resin, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or photopolymerization start. It is preferable to form from the resin composition containing an agent system.

(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 US Pat. No. 3,549,367 and a p-aminoketone, and a benzoic compound 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 as a mixture 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 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.

[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 substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). 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 simultaneous application method is 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 the form of a film is pasted with the photosensitive resin layer surface being the substrate surface side, and is pressure-bonded or heat-pressed with a roller or flat plate heated and / or pressurized using a laminator. 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.

There is no particular limitation on the substrate that is a transfer material to which the transfer material is transferred. For example, a soda glass plate having a silicon oxide film on the surface, a known glass plate such as a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic film can be used. 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.
Instead of providing an adhesive layer on the optically anisotropic layer, an adhesive layer may be provided on the material to be transferred.

[Other components]
The reflective region including the reflective layer, the transmissive region, the color filter layer, and the optical compensation layer of the transflective liquid crystal display device of the present invention can be formed by various conventionally known methods. The color filter layer or the optical compensation layer may also be formed using a transfer material. In the production of a color filter, as described in JP-A Nos. 11-248921 and 3255107, a base is formed by overlapping colored resin compositions forming 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 if necessary. In addition, the optical compensation layer may be formed of 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), an alignment film, or the like. It is preferable that the liquid crystal molecules are aligned and then fixed to the alignment state by polymerization. Specific examples of the material used in the polymerizable composition, the immobilization method, the preparation of the coating solution, and the alignment film are the same as the material and method used in forming the optically anisotropic layer.

[Other manufacturing methods]
Examples of the method for providing the optically anisotropic layer in the apparatus include the following methods in addition to using a transfer material. Applying an alignment film on the substrate on which the optically anisotropic layer is to be placed, rubbing, coating with a polymerizable liquid crystal, heating, exposing, and placing the optically anisotropic layer, or forming an alignment film on the glass substrate Method of coating, rubbing, coating containing polymerizable liquid crystal, heating, exposing to form an optically anisotropic layer, and then transferring the optically anisotropic layer to a material to be transferred via an adhesive or adhesive Is mentioned.

  A specific example of a method for manufacturing a liquid crystal display device using a transfer material 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) 28.38
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
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. The adjustment method is as follows. First, K pigment dispersion and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 1 and hydroquinone in the amounts shown in the table. Weigh out monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine, MegaFac F-176PF And 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 was 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 were 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 wire bar coater of # 5.5, and a flat 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 an air-cooled metal halide lamp (I Graphics Co., Ltd.) of 160 W / cm in the air. 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 producing 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 an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm in the air. Thus, 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 Table 1 below.

実施例１の転写材料から形成した光学異方性層は、Ｒｅ（４５０）＜Ｒｅ（５５０）＜Ｒｅ（６５９）を満足し、ほぼそれぞれの波長に対してλ／４板になっていることが確認できた。

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]
(Production of transflective LCD 1)
In Example 2, a full-color panel having the same optical configuration as that of the liquid crystal display device 1 shown in FIG. 2 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 transparent electrode)
On the color filter 1 produced above, an ITO transparent electrode film having a thickness of 1000 mm was formed by vacuum sputtering.
Film formation: After evacuating 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 mm.
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 side 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.

(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 (%)
───────────────────────────────────────
FH-2413F (Fuji Film Electromaterials Co., Ltd.) 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 placed 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 onto 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 the 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 electrodes were 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 device, and a UV curable epoxy adhesive was applied to the injection port portion and cured to obtain an ECB mode liquid crystal cell.

[Preparation of polarizing plate with optically anisotropic layer]
Next, the transfer material RET-1 produced in Example 1 is transferred onto the polarizing plate in the same process as the photosensitive resin transfer material K-1, so that the distance from the surface of the photosensitive resin layer is 100 μm. A proximity exposure machine was placed on the surface, and exposure was performed with an ultrahigh pressure mercury lamp at an irradiation energy of 100 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.
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 intended polarizing plate A with an optically anisotropic layer.

(Polarizing plate pasting)
On the back side of this 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 perpendicular to the alignment direction of the liquid crystal, and further polarized light is applied to both surfaces. A plate A was attached in such a manner that the polarizing plate absorption axis was orthogonal to the alignment direction of the liquid crystal to obtain a liquid crystal panel.
(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 3: Production of transflective LCD 2)
In Example 3, as the optical compensator for the transmissive part, a disc-shaped liquid crystalline compound was hybrid-aligned on the support, and an optical compensator for the transmissive part obtained by polymerizing this was produced, and between the panel back side substrate and the polarizing plate. 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 form a uniform liquid crystal. After forming a layer having a phase, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² were irradiated using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) 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.

A black (K) image was formed and red (R) green (G) blue (B) pixels and a color filter substrate were formed in the same procedure as in Example 2.
Further, in the same procedure as in Example 2, formation of a transparent electrode, production of a photosensitive transfer material for protrusions, formation of protrusions, formation of an opposing alignment layer, formation of a seal pattern, overlay, and liquid crystal injection were 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 A 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 2: Production of comparative transflective LCD
Also in Comparative Example 2, a full-color panel having the same optical configuration as that of the liquid crystal display device was produced. However, for comparison, a polarizing plate B with an optically anisotropic layer was formed using the transfer material RET-2 prepared in Reference Example 1.
(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, a polarizing plate B with an optically anisotropic layer was 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 2, it was approximately 267 nm.

(Contrast evaluation of transflective LCD)
Each of the transflective LCDs produced in Examples 2 and 3 and Reference Example 2 was placed in a dark room, and parallel light extracted from the 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 the front direction (normal direction) was also observed. The results are shown in Table 2.

  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 2 and 3 had less leakage light than the LCD of Reference Example 2.

Further, for the LCDs of Examples 2 and 3, 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). The result of the LCD of Example 2 is shown in FIG. 5, and the result of the LCD of Example 3 is shown in FIG. It was confirmed that the liquid crystal display device of Example 3 using the transmission part compensation layer using a discotic liquid crystal compound showed better viewing angle contrast characteristics than Example 2.

[Example 4 (transflective VA mode liquid crystal display device)]
The rod-like liquid crystal of the coating liquid LC-1 for optically anisotropic layer of Example 1 is changed to the rod-like liquid crystal represented by the above exemplary compound (110), methylethylketone is changed to chloroform, and coating liquid LC for optically anisotropic layer is obtained. -3.
Optical anisotropic produced using coating liquid LC-3 instead of the longitudinal uniaxially stretched film described in Example 1 of JP-A-2006-284703 (the longitudinally uniaxially stretched film described in [0086] of the publication) The experiment was conducted in the same manner except that the conductive film C was used. As a result, it was found that the light leakage of the transflective VA mode liquid crystal display device including the optically anisotropic film C is greatly reduced and there is almost no color shift.
The optically anisotropic film C is 1.9 μm compared to the longitudinally uniaxially stretched film having a thickness of 50 μm described in Example 1 of Japanese Patent Application Laid-Open No. 2006-284703, and can be greatly thinned.
Below, the optical characteristic of the optical anisotropic film produced using coating liquid LC-3 is shown. For reference, the optical characteristics of the coating liquid LC-1 used in the reference example are also shown.

Example 5 (Transflective TN Mode Liquid Crystal Display Device)
The same experiment was performed except that the optically anisotropic film C produced using the coating liquid LC-3 was used as the first optical anisotropic element described in Example 1 of JP-A-2004-125830. It was. It has been found that the light leakage of the transflective TN liquid crystal display device including the optically anisotropic film C is greatly reduced and there is almost no color shift.

It is a schematic sectional drawing of one Embodiment of the transflective liquid crystal display device of this invention. It is a schematic sectional drawing of other embodiment of the transflective liquid crystal display device of this invention. It is a schematic sectional drawing of some examples of the transfer material which can be used for preparation of the transflective liquid crystal display device of this invention. It is a figure which shows the reflection spectrum at the time of black display of the transflective liquid crystal display device produced in Example 2, 3 and Reference Example 2. FIG. 6 is a diagram showing contrast viewing angle characteristics of a transmission part of a transflective liquid crystal display device manufactured in Example 2. 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 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Polarizing plate 11 Optical anisotropic layer 12 Liquid crystal cell substrate 13 Counter electrode 14 Liquid crystal layer 15a Transmission electrode 15b Reflective electrode 16 Liquid crystal cell substrate 17 Optical anisotropic layer 18 Polarizing plate 19 Optical compensation layer 51 Temporary support 52 Optical anisotropic Layer 53 photosensitive resin layer 54 mechanical property control layer 55 orientation control layer 56 protective layer

Claims (10)

Optical anisotropy containing a compound represented by the following general formula (I) or (II) or a polymer containing a repeating unit derived from a compound represented by the following general formula (I) or (II) A transflective liquid crystal display device comprising at least one conductive layer:

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—, —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 nonmetallic 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;

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 for the liquid crystal core parts MG ¹ and MG ² , represented by the following formula (II) -LA or 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 transflective liquid crystal display device according to claim 1, further comprising at least one viewing angle compensation layer. 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 measured at a wavelength of 650 nm in the visible light wavelength region. The transflective liquid crystal display device according to claim 1, wherein Δnd (650 nm) satisfies Δnd (450 nm) <Δnd (550 nm) <Δnd (650 nm). The transflective liquid crystal display device according to claim 1, wherein the optically anisotropic layer is a λ / 4 plate. The transflective liquid crystal display device according to any one of claims 1 to 4, 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 surface. Transflective liquid crystal display device. 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 1, wherein the viewing angle compensation layer is provided on a surface opposite to the surface. The said viewing angle compensation layer has a layer formed by superposing | polymerizing the polymeric composition containing a disk shaped liquid crystalline compound or a rod-shaped liquid crystalline compound, The any one of Claims 1-7 characterized by the above-mentioned. The transflective liquid crystal display device described. 9. The transflective liquid crystal display device according to claim 1, wherein the liquid crystal mode is an ECB, TN, IPS, VA, or OCB mode. The transflective liquid crystal display device according to claim 1, wherein the optically anisotropic layer is a layer transferred from a transfer material.

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