JP2007108369A - Manufacturing method of liquid crystal cell substrate having TFT drive element, liquid crystal cell substrate, and liquid crystal display device - Google Patents

Abstract

Provided is a simple method for manufacturing a substrate for a liquid crystal cell having a TFT driving element that contributes to improving the color viewing angle characteristics of a liquid crystal display device.
A method of manufacturing a substrate for a liquid crystal cell having a color filter layer, a uniaxial or biaxial optically anisotropic layer, and a TFT drive element, comprising the following steps [1] to [4]: Manufacturing method including this order:
[1] A step of transferring a transfer material having a photosensitive resin layer and an optically anisotropic layer onto a temporary support onto a TFT substrate;
[2] A step of peeling the temporary support from the transfer material on the TFT substrate;
[3] A step of pattern exposing the transfer material on the TFT substrate;
[4] A step of removing unnecessary photosensitive resin layers and optically anisotropic layers on the TFT substrate by development.
[Selection] Figure 2

Description

  The present invention relates to a method for manufacturing a substrate for a liquid crystal cell having a TFT driving element, and in particular, manufacturing a substrate for a liquid crystal cell having a TFT driving element that can be used for a liquid crystal display device having excellent color viewing angle characteristics using a transfer material. The present invention relates to a method and a liquid crystal display device using the liquid crystal cell substrate.

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

  In order to improve the viewing angle characteristics, a viewing angle compensation phase difference plate (optical compensation sheet) has been applied. Until now, LCDs having excellent contrast viewing angle characteristics have been proposed by using optical compensation sheets having various optical characteristics for the various display modes described above. In particular, the three modes of OCB, VA, and IPS have wide viewing angle characteristics in all directions as wide viewing angle modes, and are already widely used in televisions for home use. In these methods using an optical compensation sheet, the contrast viewing angle characteristics can be effectively improved. Therefore, the improvement of the color viewing angle characteristics is an important issue for LCDs.

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

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

  On the other hand, although the principle is the same as that of contrast viewing angle compensation by an optical compensation sheet, a method for independently compensating for the three colors of R, G, and B has also been proposed (Patent Document 2). This is realized mainly by a method of patterning in a liquid crystal cell together with a color filter or the like. However, it has been difficult to form an optically anisotropic layer made of a material that can be patterned in a liquid crystal cell and having optically uniform retardation characteristics.

JP 2004-37837 A GB2394718

  An object of the present invention is to provide a simple method for producing a liquid crystal cell substrate having a TFT drive element and a color filter. Another object of the present invention is to provide a method for manufacturing a substrate for a liquid crystal cell having a TFT drive element and a color filter that contribute to improving the color viewing angle characteristics of a liquid crystal display device. It is another object of the present invention to provide a liquid crystal display device in which a liquid crystal cell is accurately optically compensated, has excellent productivity, and has improved color viewing angle characteristics.

Means for solving the above problems are as follows.
(1) A method for producing a substrate for a liquid crystal cell having a color filter layer, a uniaxial or biaxial optically anisotropic layer, and a TFT drive element, wherein the color filter layer and the optically anisotropic layer are A manufacturing method including a step of providing using a transfer material.
(2) The optically anisotropic layer is a layer formed by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then fixing by irradiation with heat or ionizing radiation. The manufacturing method as described in (1).
(3) The production method according to (2), wherein the ionizing radiation is polarized ultraviolet rays.
(4) The production method according to any one of (1) to (3), wherein the reactive group is an ethylenically unsaturated group.
(5) The manufacturing method according to any one of (1) to (4), wherein the liquid crystalline compound is a rod-like liquid crystal.
(6) The manufacturing method according to any one of (1) to (4), wherein the liquid crystalline compound is a discotic liquid crystal.
(7) The front retardation (Re) of the optically anisotropic layer is not substantially 0, and the in-plane slow axis is the tilt axis (rotation axis) with respect to the normal direction of the optically anisotropic layer. With respect to the normal direction of the optically anisotropic layer with the retardation value measured by making light of wavelength λ nm incident from the direction inclined + 40 ° and the in-plane slow axis as the tilt axis (rotation axis) The production method according to any one of (1) to (6), wherein retardation values measured by making light having a wavelength λ nm incident from a direction inclined by 40 ° are substantially equal.
(8) The front retardation (Re) of the optically anisotropic layer is 60 to 200 nm, the in-plane slow axis is the tilt axis (rotation axis), and + 40 ° with respect to the normal direction of the optically anisotropic layer. The production method according to any one of (1) to (7), wherein a retardation value measured by making light having a wavelength λ nm incident from an inclined direction is 50 to 250 nm.
(9) The manufacturing method according to any one of (1) to (8), wherein the liquid crystal cell substrate further includes a pixel electrode, and the optically anisotropic layer includes the pixel electrode. The manufacturing method formed in the said TFT drive element side rather than.
(10) The manufacturing method according to any one of (1) to (9), wherein the optical anisotropic layer is provided with a through hole for electrical connection with the driving element.
(11) The manufacturing method according to any one of (1) to (10), including the following steps [1] to [4] in this order:
[1] A step of transferring a transfer material having a photosensitive resin layer and an optically anisotropic layer onto a temporary support onto a TFT substrate;
[2] A step of peeling the temporary support from the transfer material on the TFT substrate;
[3] A step of pattern exposing the transfer material on the TFT substrate;
[4] A step of removing unnecessary photosensitive resin layers and optically anisotropic layers on the TFT substrate by development.
(12) A liquid crystal cell substrate manufactured by the manufacturing method according to any one of (1) to (11).
(13) A liquid crystal cell substrate having a color filter layer and an optically anisotropic layer formed in the same pattern as the colored pattern of the color filter layer on a TFT substrate.
(14) A liquid crystal cell having the liquid crystal cell substrate according to (12) or (13).
(15) A liquid crystal display device having the liquid crystal cell according to (14).
(16) The liquid crystal display device according to (15), wherein the liquid crystal mode is either VA or IPS.

According to the manufacturing method of the present invention, a liquid crystal display device including an optically anisotropic layer having an optical compensation capability in a liquid crystal cell can be manufactured without increasing the number of manufacturing steps of the liquid crystal display device. That is, the optically anisotropic layer that has been provided by the bonding method together with the polarizing plate on the outside of the substrate for the liquid crystal display device so far can be provided on the inside of the substrate with almost no increase in manufacturing steps. become. This can reduce the cost required for the rework of the bonding process, and concentrate the functions from the member to the substrate while obtaining good optical characteristics, thereby reducing the total manufacturing cost and increasing the added value Can do. In addition, by manufacturing a liquid crystal cell substrate having a color filter and a TFT drive element by a method using a transfer material instead of a conventional photolithography method, it is possible to reduce the manufacturing cost by reducing the resist coating and peeling process. . Furthermore, a liquid crystal display device having a liquid crystal cell substrate produced by the production method of the present invention has improved display quality, particularly color viewing angle characteristics.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  In 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, with light having a wavelength of λ nm incident in the normal direction of the film. 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.

[Transfer material]
The transfer material used in the production method of the present invention has at least one optically anisotropic layer and at least one layer forming a photosensitive resin layer on a temporary support. FIG. 1 is a schematic cross-sectional view of several examples of transfer materials. The transfer material shown in FIG. 1A has an optically anisotropic layer 12 and a photosensitive resin layer 13 on a transparent or opaque temporary support 11. The transfer material may have other layers. For example, as shown in FIG. 1B, the unevenness on the counterpart substrate side is transferred between the temporary support 11 and the optically anisotropic layer 12 during transfer. 1 may be provided with a layer 14 for controlling mechanical properties such as cushioning properties for absorbing water or imparting unevenness follow-up, and as shown in FIG. A layer 15 functioning as an alignment layer for controlling the alignment of the liquid crystalline molecules therein may be disposed, or both layers may be provided as shown in FIG. Moreover, you may provide the protective layer 16 which can peel in the outermost surface for the objectives, such as surface protection of the photosensitive resin layer of FIG.1 (e).

[Transfer substrate for liquid crystal display]
The transfer material is transferred to a TFT substrate (in this specification, “TFT substrate” means a substrate in which a TFT drive element is provided on a substrate to be transferred (support)), and the optical characteristics of the liquid crystal cell. A liquid crystal cell substrate having a TFT driving element having an optically anisotropic layer for compensation can be formed. The obtained liquid crystal cell substrate is used as one of a pair of liquid crystal cell substrates as a TFT array substrate. FIG. 2 is a schematic cross-sectional view of an example of a TFT array substrate (TFT substrate with an optically anisotropic layer) produced by the production method of the present invention. The substrate to be transferred (support) 21 is not particularly limited as long as it is transparent, but preferably has a small birefringence, and glass, a low birefringence polymer, or the like is used.
In general, a gate electrode 22-1, a gate insulating film 22-2, an island 22-3 made of an amorphous silicon layer and an n ⁺ amorphous silicon layer, source and drain electrodes (22-4 and 22- 5) are sequentially formed, and the n ⁺ amorphous silicon in the channel portion is further etched, and further, a protective insulating film 22-6 is provided thereon to provide the TFT driving element 22. A transfer material is transferred thereon, mask exposure is performed, and development is performed to form a through hole 27. Further, the color filter layer 23 and the optically anisotropic layer 24 made of a photosensitive resin layer are patterned into a desired shape by repeating transfer, pattern exposure, and development processes using a plurality of transfer materials, and the color filter layer An optically anisotropic layer is provided simultaneously. A transparent electrode layer 25 is formed through the through hole. Although FIG. 2 shows a mode in which the pixel electrode is formed above the color filter layer, it may be formed below the color filter layer, as is often seen recently. Although there may be other layers transferred from the transfer material on the optically anisotropic layer 24, it is necessary to prevent impurities from entering the liquid crystal cell as much as possible. It is preferred that it be removed from time to time. A transparent electrode layer 25 is formed on the optically anisotropic layer 24, and an alignment layer 26 for aligning liquid crystal molecules in the liquid crystal cell is formed thereon.
Since the color filter layer and the optically anisotropic layer are simultaneously formed in one transfer-exposure-development process by the production method of the present invention using the transfer material, the viewing angle characteristics of the liquid crystal display device can be obtained with the same number of steps. Can be improved.

[Liquid Crystal Display]
FIG. 3 is a schematic sectional view showing an example of the liquid crystal display device of the present invention. The example of FIG. 3 is a liquid crystal display device using a liquid crystal cell 37 in which the TFT array substrate of FIG. 2 is used as a lower substrate and a liquid crystal 31 is sandwiched between a counter substrate 32. On both sides of the liquid crystal cell 37, a polarizing plate composed of a polarizing layer 33 sandwiched between two cellulose ester films 34 and 35 is disposed. The cellulose ester film 35 on the liquid crystal cell side may be used as an optical compensation sheet or may be the same as 34. Although not shown in the drawing, in the aspect of the reflective liquid crystal display device, only one polarizing plate is required on the observation side, and a reflective film is provided on the back surface of the liquid crystal cell or on the inner surface of the lower substrate of the liquid crystal cell. Of course, a front light can be provided on the liquid crystal cell observation side. Further, a transflective type in which a transmissive portion and a reflective portion are provided in one pixel of the display device is also possible. The display mode of the present liquid crystal display device is not particularly limited, and can be used for all transmissive and reflective liquid crystal display devices. In particular, the present invention is effective for the VA mode where color viewing angle characteristics are desired to be improved.

The optically anisotropic layer in the liquid crystal cell substrate obtained by the production method of the present invention contributes to the optical compensation of the cell of the liquid crystal display device, that is, enlarges the contrast viewing angle and eliminates the image coloring of the liquid crystal display device. To contribute. By the manufacturing method of the present invention using a transfer material, the retardation film and the color filter layer can be simultaneously transferred to the TFT substrate. As a result, the field of view of the liquid crystal display device can be changed without changing the manufacturing cost of the liquid crystal display device. Angular characteristics, particularly color viewing angle characteristics and transmittance can be improved.
Hereinafter, the transfer material used in the production method of the present invention will be described in detail with respect to the material used for production, the production method, etc., but the present invention is not limited to this aspect, and other aspects, It can be produced with reference to the following description and conventionally known methods.

[Temporary support]
The temporary support used for the transfer material may be transparent or opaque and is not particularly limited. Examples of the polymer constituting the support include cellulose ester (eg, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate), polyolefin (eg, norbornene-based polymer), poly (Meth) acrylic acid ester (eg, polymethyl methacrylate), polycarbonate, polyester and polysulfone, and norbornene-based polymer are included. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and from the viewpoint of low birefringence, cellulose ester and norbornene are preferred. 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 in the transfer material is not particularly limited as long as it has at least one incident direction in which Re is not substantially zero when the phase difference is measured, that is, has optical characteristics that are not isotropic. From the viewpoint of easy control of the optical characteristics used in the liquid crystal cell, a layer formed by curing the liquid crystal layer containing at least one liquid crystalline compound by irradiating with ultraviolet rays is desirable.

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

  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 this embodiment, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. Since the change in temperature and humidity can be reduced, it is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group. In the case of a mixture, at least one of the reactive groups in one liquid crystal molecule is formed. Is more preferably 2 or more. The liquid crystalline compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups. The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

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

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

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

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

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

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

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

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

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

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

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

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

  Preferred examples of the discotic compound are shown below.

  The optically anisotropic layer is formed by applying a composition containing a liquid crystal compound (for example, a coating solution) to the surface of an alignment layer described later to obtain an alignment state exhibiting a desired liquid crystal phase, and then heating the alignment state. Or it is preferable that it is the layer produced by fixing by irradiation of ionizing radiation. It is preferable that the optically anisotropic layer exhibits biaxiality because a liquid crystal cell, particularly a VA mode liquid crystal cell, can be optically compensated accurately. 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). Any of them can be used in the present invention.

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

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

  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 the solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Fixation of alignment state of liquid crystalline compounds]
The aligned liquid crystalline compound is preferably fixed while maintaining the alignment state. The immobilization is preferably carried out by a polymerization reaction of a reactive group introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).

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

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

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

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

  In the production method of the present invention, when the optically anisotropic layer and the color filter layer are formed by transferring the transfer material to the TFT substrate, the optical characteristics of the optically anisotropic layer are R light, G It is preferable that the optical characteristics are adjusted to be optimal for optical compensation when light and B light are incident. That is, when the photosensitive resin layer is colored red and the transfer material is used to form the R layer of the color filter, the optical characteristics of the optically anisotropic layer of the transfer material are optimal for optical compensation when R light is incident. When the photosensitive resin layer is colored green and the transfer material is used for forming the G layer of the color filter, the optical characteristics of the optical anisotropic layer of the transfer material are optical compensation when G light is incident. In contrast, when the photosensitive resin layer is colored blue and the transfer material is used for forming the B layer of the color filter, the optical characteristics of the optically anisotropic layer of the transfer material are the same as when B light is incident. It is preferably adjusted optimally for optical compensation. The optical properties of the optically anisotropic layer are adjusted to a preferable range depending on, for example, the type of liquid crystalline compound, the type or addition amount of the alignment agent, the type of alignment film, the rubbing treatment conditions of the alignment film, or the polarization irradiation conditions. Can do.

  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. The horizontal plane of the board and the transparent support is said to be parallel, but it is not required to be strictly parallel. In the present specification, an orientation with an inclination angle of less than 10 degrees with the horizontal plane is meant. And The inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.

  Hereinafter, the following general formulas (1) to (3) will be described in order.

式中、Ｒ¹、Ｒ²およびＲ³は各々独立して、水素原子または置換基を表し、Ｘ¹、Ｘ²およびＸ³は単結合また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また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および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のアルキル基または水素原子）、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−およ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−および−ＳＯ₂−からなる群より選ばれる二価の連結基また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 listed 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 preferably the substituents 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-2005-099248 can be used, and the synthesis method of these compounds is also described in the specification. ing.

  The amount of the compound represented by the general formulas (1) to (3) is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass based on the mass of the liquid crystal compound. 02-1 mass% is especially preferable. In addition, the compounds represented by the general formulas (1) to (3) may be used alone or in combination of two or more.

[Alignment layer]
As described above, an alignment layer may be used to form the optically anisotropic layer. The alignment layer is generally provided on a transparent support or an undercoat layer coated on the transparent support. The alignment layer functions so as to define the alignment direction of the liquid crystal compound provided thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer. Preferred examples of the alignment layer include a rubbing-treated layer of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, 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 preferable polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).

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

  A polyimide film (preferably fluorine atom-containing polyimide) widely used as an alignment layer for LCD is also preferable as the organic alignment layer. 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. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted 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.

  In the transfer material, the optically anisotropic layer can be transferred by aligning the liquid crystalline compound on the temporary alignment layer, fixing the alignment, and then using an adhesive on the transparent support. From the viewpoint of property, it is preferable to form directly without transfer.

[Photosensitive resin layer]
The photosensitive resin layer used for the transfer material is made of a photosensitive resin composition, and if the transfer property to the substrate is different between the exposed part and the unexposed part when irradiated with light through a mask or the like, the positive type is also used. It may be a negative type and is not particularly limited. The photosensitive resin layer comprises at least (1) an alkali-soluble resin, (2) a monomer or oligomer, (3) a photopolymerization initiator or photopolymerization initiator system, and (4) a colorant such as a dye or pigment. It is preferable to form from the coloring resin composition containing these.
Hereinafter, the components (1) to (4) will be described.

(1) Alkali-soluble resin The alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. The binder polymer having these polar groups may be used alone or in the form of a composition used in combination with a normal film-forming polymer, and the content relative to the total solid content of the colored resin composition 20-50 mass% is common, and 25-45 mass% is preferable.

(2) Monomer or oligomer The monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. . 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, hexa Diol 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 JP-B-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 for the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is disclosed. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 Trihalomethyl described in Saisho - 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.

(4) Colorant Known colorants (dyes and pigments) can be added to the colored resin composition. In the case of using a pigment among the known colorants, it is desirable that the pigment is uniformly dispersed in the colored resin composition. Therefore, the particle size is preferably 0.1 μm or less, particularly preferably 0.08 μm or less. .
Examples of the known dye or pigment include pigments described in paragraph No. [0033] of JP-A No. 2004-302015 and column 14 of US Pat. No. 6,790,568.

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

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

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

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

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

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

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

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

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

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

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 18, and m represents an integer of 2 to 14. p and q represent integers of 0 to 18, but are not included when both p and q are simultaneously 0.

A particularly preferred surfactant represented by the general formula (a) is referred to as a monomer (a), and a monomer represented by the general formula (b) is referred to as a monomer (b). C _m F _{2m + 1} shown in the general formula (a) may be linear or branched. m shows the integer of 2-14, Preferably it is an integer of 4-12. The content of C _m F _{2m + 1} is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, based on the monomer (a). R ₁ represents a hydrogen atom or a methyl group. Moreover, n shows 1-18, and 2-10 are preferable especially. R ₂ and R ₃ shown in the general formula (b) each independently represent a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each represent an integer of 0 to 18, but p and q do not include 0. p and q are preferably 2 to 8.

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

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

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

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

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

  Specific examples of preferable fluorine-based surfactants include compounds described in paragraph numbers [0054] to [0063] of JP-A No. 2004-163610. Moreover, the following commercially available surfactant can also be used as it is. Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants are listed. be able to. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant.

[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-alkoxy Chill 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 that are 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 coating, air knife coating, curtain coating, roller coating, 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 method of simultaneous application 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 color filter layer / optically anisotropic layer using transfer material]
The method for transferring the transfer material onto the substrate 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 formed in the form of a film can be attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the photosensitive resin surface facing the substrate surface. 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.

  As a substrate for transferring the transfer material, for example, a transparent substrate, that is, a known glass plate such as a glass plate having an insulating film such as silicon oxide or silicon nitride on its surface, low expansion glass, non-alkali glass, quartz glass plate, Alternatively, a driving TFT (thin film transistor array) for applying a voltage to the liquid crystal on a plastic film or the like can be used. Moreover, the said board | substrate can make close_contact | adherence with the photosensitive resin layer favorable by performing a coupling process previously. 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.

A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposure is performed from above the mask through the mask, followed by development with a developer. A contact pattern that exposes the underlying electrode is formed by development, and a specific colored resin layer, for example, a laminate of a red (R) resin layer and an optically anisotropic layer is disposed on the substrate at a predetermined position. A patterned R color is formed. A color filter and an optically anisotropic layer formed in the same pattern as the RGB pattern by performing the same process using a transfer material having a green (G) resin layer and a blue (B) resin layer, respectively A TFT substrate having a color filter with an optically anisotropic layer having the above can be obtained. Here, as the light source for exposure, any light source capable of irradiating light in a wavelength region capable of curing the resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 10-5000 mJ / cm < ² > normally, Preferably it is about 20-500 mJ / cm < ² >.

Moreover, there is no restriction | limiting in particular as a developing solution used for the image development process after exposure, Well-known developing solutions, such as the thing of Unexamined-Japanese-Patent No. 5-72724, can be used. In addition, the developer preferably has a resin layer exhibiting a dissolution type development behavior. For example, a developer containing a compound having a pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L is preferred, but further developability is improved. Therefore, an organic solvent may be added. Organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone , Ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone, tetrahydrofuran, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 60% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

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

  In the production of a color filter, as described in JP-A-11-248921 and Japanese Patent No. 3255107, a base is formed by overlapping colored resin compositions that form a color filter, and a transparent electrode is formed thereon. In addition, it is preferable from the viewpoint of cost reduction that the spacers are formed by overlapping the protrusions for split orientation as necessary.

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

(Preparation of coating liquid CU-1 for thermoplastic resin layer)
The following composition was prepared, filtered through a polypropylene filter having a pore size of 30 μm, and used as a coating liquid CU-1 for a thermoplastic resin 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 (made 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 LC-1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as the coating liquid LC-R1 for the optically anisotropic layer.

LC-1-1 was obtained from Tetrahedron Lett. It was synthesized according to the method described in Journal, Vol. 43, page 6793 (2002). LC-1-2 was synthesized by the method described in EP1388538A1, page 21.
─────────────────────────────────――
Coating composition for optically anisotropic layer (%)
─────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 28.6
Chiral agent (Paliocolor LC756, BASF Japan)
3.40
4,4′-Azoxydianisole 0.52
Styreneboronic acid 0.02
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.36
Methyl ethyl ketone 66.0
─────────────────────────────────――

(Preparation of coating liquid LC-2 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-2 for an optically anisotropic layer. LC-2-1 was synthesized by the method described in JP-A No. 2001-166147. LC-2-2 was prepared by dissolving commercially available hydroxyethyl methacrylate, acrylic acid, and M5610 (manufactured by Daikin Industries, Ltd.) in methyl ethyl ketone at a weight ratio of 15/5/80 (concentration 40%). As V-601 (manufactured by Wako Pure Chemical Industries, Ltd.). LC-2-3 first introduced octyloxybenzoic acid (manufactured by Kanto Chemical Co., Ltd.) into excess hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) by the mixed acid anhydride method to obtain a monoacylphenol compound. . Subsequently, methyl p-hydroxybenzoate was hydroxyethylated with ethylene carbonate, ester hydrolysis, and bromination with hydrobromic acid to synthesize 2-bromoethyloxybenzoic acid. These two compounds were converted to diesters by esterification by the mixed acid anhydride method, and then quaternized with dimethylaminopyridine to synthesize LC-2-3, which is an onium salt.
─────────────────────────────────――
Coating liquid composition for optically anisotropic layer (% by mass)
─────────────────────────────────――
Discotic liquid crystalline compound (LC-2-1) 30.0
Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 3.3
Photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.0
Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.33
Air interface side vertical alignment agent (LC-2-2) 0.12
Alignment layer side vertical alignment agent (LC-2-3) 0.15
Methyl ethyl ketone 65.1
─────────────────────────────────――

  A method for producing a coating solution for the photosensitive resin layer will be described below. Table 1 shows the composition of each coating solution for the photosensitive resin layer.

The compositions in Table 1 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
──────────────────────────────────――

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

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

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

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

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

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

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

(Preparation of coating solution PP-K1 for photosensitive resin layer)
The coating solution PP-K1 for the photosensitive resin layer first weighs the K pigment dispersion and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, mixes at a temperature of 24 ° C. (± 2 ° C.), and stirs at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3- Weigh out bromophenyl] -s-triazine and surfactant 1 MegaFac F-176PF, add them in this order at a temperature of 25 ° C. (± 2 ° C.), and stir at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. Obtained by.

(Preparation of coating solution PP-R1 for photosensitive resin layer)
The coating liquid PP-R1 for the photosensitive resin layer was first weighed in the amounts of R pigment dispersion-1, R pigment dispersion-2 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, and the temperature was 24 ° C. (± 2 ° C. ) And stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxax as shown in Table 1 Diazole, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine were weighed out and the temperature was 24 ° C. (± 2 In this order and stirred at 150 rpm for 10 minutes, then weighed out the amount of ED152 listed in Table 1 and mixed at a temperature of 24 ° C. (± 2 ° C.) to 150 rpm. Stir for 0 minutes, and then weigh out the amount of surfactant 1 MegaFac F-176PF listed in Table 1, add it at a temperature of 24 ° C. (± 2 ° C.), stir at 30 rpm for 30 minutes, and filter through nylon mesh # 200. Was obtained by

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

(Preparation of coating solution PP-B1 for photosensitive resin layer)
The photosensitive resin layer coating solution PP-B1 was first weighed in the amounts of CF Blue EX3357, CF Blue EX3383 and propylene glycol monomethyl ether acetate listed in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.) and 150 rpm 10 Stir for minutes, then weigh out the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole, phenothiazine as listed in Table 1, Add in this order at a temperature of 25 ° C. (± 2 ° C.), stir at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes, and then weigh out the amount of the surfactant 1 megafac F-176PF shown in Table 1 The mixture was added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200.

(Polarized UV irradiation device POLUV-1)
A microwave emission type ultraviolet irradiation device (Light Hammer 10, 240 W / cm, manufactured by Fusion UV Systems) equipped with D-Bulb having a strong emission spectrum at 350 to 400 nm as a UV light source was separated from the irradiation surface by 3 cm. At the position, a wire grid polarizing filter (ProFlux PPL02 (high transmittance type), manufactured by Moxtek) was installed to produce a polarized UV irradiation apparatus. The maximum illuminance of this device was 400 mW / cm ² .

(Production of photosensitive resin transfer material for RGB)
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 intermediate layer / alignment layer coating solution 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-R1 for optically anisotropic layer is applied thereon with a # 6 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 polarized UV using POLUV-1 so that the transmission axis of the polarizing plate was in the TD direction of the transparent support in a nitrogen atmosphere having an oxygen concentration of 0.3% or less. (An illuminance of 200 mW / cm ² and an irradiation amount of 200 mJ / cm ² ) was used to immobilize the optical anisotropic layer to form an optically anisotropic layer having a thickness of 2.8 μm. Finally, the photosensitive resin composition PP-R1 is applied and dried to form a photosensitive resin layer having a thickness of 2.0 μm, and R photosensitive resin transfer material R-1 which is Example 1 of the present invention is formed. Produced.
For G and B, PP-G1 and PP-B1 were used instead of PP-R1, and the optical anisotropic layer coating bars were set to # 6 and # 5, respectively, and LC-G1 and LC-B1 were applied. In the same manner, photosensitive resin layers G-1 and B-1 for G and B, which are Examples 2 and 3, respectively, were formed. The optically anisotropic layers of G-1 and B-1 were 2.75 μm and 2.3 μm, respectively.

(Phase difference measurement)
By the parallel Nicol method using a fiber-type spectrometer, the front retardation Re (0) at the wavelength λ and the retardations Re (40), Re (−) when the sample is tilted ± 40 degrees around the slow axis as the rotation axis. 40) was measured. For R, G, and B, λ was measured for retardation of 611 nm, 545 nm, and 435 nm, respectively. The phase difference of the optically anisotropic layer is obtained by calibrating with the transmittance data of the color filter measured in advance, so that only the phase difference of the optically anisotropic layer having the phase difference is obtained from the transfer material solid-transferred onto the glass. It was. Table 1 shows the phase difference measurement results of Examples 1 to 3.

(Production of TFT substrate)
A TFT substrate was produced by the following method. A process image is shown in FIG.
-Formation of gate electrode-
Washing: The alkali-free glass substrate was washed with a rotating brush having nylon bristles while sprayed with a detergent solution such as semicocrine adjusted to 25 ° C. by a shower, and washed with a pure water shower. Thereafter, the water was dried with a high-pressure air knife using dry air, and the mixture was dried.
Film formation: performed by a vacuum sputtering film formation apparatus. After evacuation to about 10 ⁻⁴ Pa in a vacuum chamber, the substrate is heated to 300 ° C. with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ⁻¹ Pa, and Cr is blown off from the target surface. Deposited to thickness.

Photolithograph: A Cr film was patterned into a desired electrode shape by a photolithography method. A photoresist for TFT (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 furnace, a pattern was baked using a photomask having a desired pattern with an exposure apparatus (Nikon Corporation stepper). 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 then post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, etching is performed while spraying with a swinging shower head with a Cr etching solution (containing cerium ammonium nitrate: manufactured by Kanto Chemical Co., Inc.), and it is confirmed that the Cr film has been sufficiently dissolved, and etching is performed with a pure water shower. The liquid was washed off, and the water was 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 gate insulating film and amorphous silicon film-
Formation of lower insulating layer: A SiO ₂ film was formed by a vacuum sputtering film forming apparatus. After evacuating to about 10 ⁻⁵ Pa in a vacuum chamber, the substrate is heated to 280 ° C. with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ⁻¹ Pa, and SiO ₂ is blown off from the target surface. The film was deposited until the thickness became.
Washing: Pure water adjusted to 25 ° C. was washed with a rotating brush having nylon bristles while being sprayed by a shower, and dried with a high-pressure air knife using dry air.

Three-layer continuous film formation: A silicon nitride film, an amorphous silicon film, and an n ⁺ amorphous silicon film were sequentially deposited by a plasma CVD apparatus (manufactured by AKT). The substrate was placed in a load lock chamber, evacuated to 10 ⁻⁴ Pa, and then heated to 300 ° C. The silicon nitride was maintained at 3 Pa with exhaust resistance while controlling the flow rate of SiH ₄ , NH ₃ , and N ₂ at 1: 1: 5 by mass flow. Glow discharge (low temperature plasma) was generated by applying a high frequency of 1 kw / 13.56 MHz with an electrode distance of 40 mm to generate radicals and deposit a silicon nitride film on the substrate surface. Once 4000 A was deposited, the gas was turned off and kept in a high vacuum state. Next, an amorphous silicon film was deposited. The substrate temperature was 300 ° C., SiH ₄ and H ₂ were flow controlled at a ratio of 1: 5, plasma was generated at 150 Pa RF with a pressure of 1 Pa, and about 300 nm was deposited. Next, an n ⁺ amorphous silicon film was deposited. The substrate temperature is 300 ° C., SiH ₄ , PH ₃ (3% dilution), H ₂ are flow controlled at a ratio of 1: 1: 5, and plasma is generated with 150 W RF at a pressure of 1 Pa to deposit about 50 nm. It was.

-Island patterning-
Photolithography: Amorphous silicon and an n ⁺ amorphous silicon film were patterned into an island shape on the gate electrode by a photolithography method. A photoresist for TFT (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 furnace, a pattern was baked using a photomask having a desired pattern with an exposure apparatus (Nikon Corporation stepper). 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 then post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, the amorphous silicon and n ⁺ amorphous silicon films were dry etched. Using an RIE apparatus, etching was performed while maintaining a selectivity with SiNx under the conditions of SF ₆ gas (40 SCCM), 0.4 Pa pressure, RF power 1500 W, and bias 400 W.
Next, the resist was peeled off by applying a roll brush while spraying a resist stripping solution (containing 2-aminoethanol and NMP: manufactured by Tokyo Ohka Kogyo Co., Ltd.) with a shower head. The stripping solution was swept away with a hot water shower and an air knife.

―Drain electrode patterning―
Washing: Pure water adjusted to 25 ° C. was washed with a rotating brush having nylon bristles while being sprayed by a shower, and dried with a high-pressure air knife using dry air.
Film formation: Performed with a vacuum sputtering film forming apparatus. After evacuating to about 10 ⁻⁴ Pa in a vacuum chamber, the substrate is heated to 300 ° C. with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ⁻¹ Pa, and Cr is blown off from the target surface. Deposited to thickness.
Photolithograph: A photoresist for TFT (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 furnace, a pattern was baked using a photomask having a desired pattern with an exposure apparatus (Nikon Corporation stepper). 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 then post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, etching is performed while spraying with a swinging shower head with a Cr etching solution (containing cerium ammonium nitrate: manufactured by Kanto Chemical Co., Inc.). After confirming that the Cr film is sufficiently dissolved, the etching solution is washed off with a pure water shower. The water was 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.
-Channel etching-: The n + amorphous silicon layer between the drain electrodes is removed by etching. Since selective etching cannot be performed, the digging depth is controlled by the etching time. Using an RIE apparatus, etching was performed for 40 seconds under the conditions of SF6 gas (40 SCCM), a pressure of 0.4 Pa, an RF power of 500 W, and a bias of 100 W.

(Formation of passivation layer)
Washing: Pure water adjusted to 25 ° C. was washed with a rotating brush having nylon bristles while being sprayed by a shower, and dried with a high-pressure air knife using dry air.
Formation of protective insulating film: A silicon nitride film was deposited by a plasma CVD apparatus (manufactured by AKT). The substrate was placed in a load lock chamber, evacuated to 10 ⁻⁴ Pa, and then heated to 280 ° C. The silicon nitride was maintained at 3 Pa with exhaust resistance while controlling the flow rate of SiH ₄ , NH ₃ , and N ₂ at 1: 1: 5 by mass flow. Glow discharge (low temperature plasma) was generated by applying a high frequency of 1 kw / 13.56 MHz at a distance of 40 mm between the electrodes, generating radicals, and depositing 200 nm of a silicon nitride film on the substrate surface.
Contact hole patterning: A TFT 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 furnace, a pattern was baked using a photomask having a desired pattern with an exposure apparatus (Nikon Corporation stepper). 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 then post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, etching is performed by immersing in a dip tank filled with an SiNx etching solution (BHF: buffered hydrofluoric acid contained: manufactured by Kanto Chemical Co., Inc.), washing off the etching solution with a pure water shower, and water with a high pressure air knife using dry air. After cutting and drying, the resist was peeled off with a roll brush while spraying a resist stripping solution (containing 2-aminoethanol and NMP: manufactured by Tokyo Ohka Kogyo Co., Ltd.) with a shower head. The stripping solution was swept away with a hot water shower and an air knife.

(Transfer of RGB transfer material to TFT substrate)
The TFT substrate was washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower. After pure water shower washing, a silane coupling solution (N-β (aminoethyl) γ -Aminopropyltrimethoxysilane 0.3% aqueous solution, 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 material (PP-R1), a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) was used, and the substrate was heated at 100 ° C. for 2 minutes to a rubber roller temperature of 130. Lamination was performed at a temperature of 100 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 2.2 m / min.
After peeling off the protective film, the exposure mask surface with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (Hitachi Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp. The photosensitive resin layer was exposed to a pattern having a contact hole in a portion corresponding to the source electrode with a stripe pattern corresponding to the R pixel at 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 Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer / alignment layer.
Subsequently, a sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T- CD1, manufactured by Fuji Photo 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 and stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) at a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a shower and a rotating brush with nylon bristles to obtain a through-hole pattern, which was further post-exposed to the substrate from the resin layer side with an ultrahigh pressure mercury lamp at a light of 500 mJ / cm ^2. Thereafter, heat treatment was performed at 220 ° C. for 15 minutes.
Similarly, the photosensitive resin materials (PP-G1, PP-B1,) are also exposed and developed in a stripe pattern corresponding to the G and B pixels, respectively, and having a contact hole in a portion corresponding to the source electrode. did.
The substrate on which the RGB pattern was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.
(Formation of transparent electrode)
A transparent electrode film was formed by sputtering ITO on the TFT substrate on which the insulating layer and the optically anisotropic layer produced above were transferred and patterned.
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. And deposited to a thickness of 100 nm.
Photolithograph: A photoresist for TFT (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 furnace, a pattern was baked using a photomask having a desired pattern with an exposure apparatus (Nikon Corporation stepper). 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 then 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. As the alignment material, polyimide JALS204 manufactured by JSR Co., Ltd. was used, and it was selectively applied to the region where the pixel electrodes were arranged by a roll coating method. After coating, prebaking was performed for 15 minutes in an atmosphere at 80 ° C., 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.

(Preparation of opposite substrate)
A counter substrate was prepared having a gap control column pattern and an alignment control projection pattern in a desired shape on a common electrode formed of a transparent conductive film.
(Formation of facing side alignment layer)
A polyimide alignment layer was formed on the transparent conductive layer in the same manner as the TFT array substrate. As the alignment material, polyimide JALS204 manufactured by JSR Co., Ltd. was used, and it was selectively applied to the region where the pixel electrodes were arranged by a roll coating method. After coating, prebaking was performed for 15 minutes in an atmosphere at 80 ° C., 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.
(Seal pattern formation)
A seal pattern is formed around the TFT substrate. An epoxy resin containing 1% by mass of spacer particles (Structure Bond XN-21S manufactured by Nissan Chemical Industries, Ltd.) is opened in a predetermined area surrounding the display area with a seal dispenser device in a form corresponding to a liquid crystal injection port. Printed. This was calcined at 80 ° C. for 30 minutes.
(Overlapping)
The TFT substrate and the counter substrate were aligned with an overlapping device while being aligned so that they overlap at the correct position. In this state, while applying a pressure of 0.03 MPa, the bonded glass substrate was heat-treated at 180 ° C. for 90 minutes to cure the sealing agent, thereby obtaining a laminate of two glass substrates. A balloon-type baking apparatus was used for baking.
(Liquid crystal injection)
A liquid crystal material was injected into the glass substrate laminate using a liquid crystal injection device. The liquid crystal material was MLC-6608 manufactured by Merck & Co., Inc., which was put in a liquid crystal dish and degassed together with the substrate laminate in a vacuum chamber for 60 minutes under a vacuum of 10 ⁻¹ Pa. After sufficiently evacuating the vacuum, the portion of the inlet provided in the seal was immersed in the liquid crystal and then returned to atmospheric pressure and held for 180 minutes to fill the gap between the glass substrates with the liquid crystal. Thereafter, the substrate laminate was taken out from the injection apparatus, and a UV curable epoxy adhesive was applied to the injection port portion and cured to obtain a liquid crystal cell.
(Polarized plate pasting)
A polarizing plate HLC2-2518 (manufactured by Sanritz Co., Ltd.) was attached to both sides of the liquid crystal cell in an arrangement in which the absorption axes were orthogonal to each other to obtain a liquid crystal panel.

(Production of VA-LCD of Example 4)
As a cold-cathode tube backlight for a color liquid crystal display device, a phosphor in which BaMg ₂ Al ₁₆ O ₂₇ : Eu, Mn and LaPO ₄ : Ce, Tb are mixed at a weight ratio of 50:50 is green (G), Y ₂ O ₃ : Eu was red (R) and BaMgAl ₁₀ O ₁₇ : Eu was blue (B) to produce a white three-wavelength fluorescent lamp having an arbitrary color tone. A liquid crystal cell provided with the above polarizing plate was placed on the backlight, and a VA-LCD of Example 4 was produced.

(Production of VA-LCD of Comparative Example 1)
There was no optically anisotropic layer in the transfer material. Instead, an optically anisotropic layer of G-1 was produced using AL-1 and LC-G1 on the protective film on the liquid crystal cell side of the lower polarizing plate. A VA-LCD of Comparative Example 1 was produced in the same manner as in Example 4 except that a 2.75 μm optically anisotropic layer was formed by the same method as in Example 1.

(Optical characteristics of VA-LCD)
The viewing angle characteristics of the manufactured liquid crystal display device were measured with a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM). About Example 4 and Comparative Example 1 on the xy chromaticity diagram when the viewing angle is changed by 0 to 80 degrees in the right direction, the upper right 45 degrees direction, and the upward direction from the front of the LCD during black display (no voltage applied) FIG. 4 shows the color change in FIG. 4, and Table 3 shows the result of visual evaluation, particularly in the direction of 45 degrees obliquely upward to the right.

It is a schematic sectional drawing of an example of the transfer material used for the manufacturing method of this invention. It is a schematic sectional drawing of an example of the board | substrate for liquid crystal cells (TFT array substrate) obtained by the manufacturing method of this invention. It is a schematic sectional drawing of an example of the liquid crystal display device which has the board | substrate for liquid crystal cells obtained by the manufacturing method of this invention. FIG. 10 is a diagram showing color viewing angle characteristics of a VA-LCD manufactured in Example 4. It is a figure which shows the process of TFT substrate preparation.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Temporary support body 12 Optically anisotropic layer 13 Photosensitive resin layer 14 Mechanical property control layer 15 Orientation control layer 16 Protective layer 21 Transfer substrate (support body)
22 TFT drive element 22-1 Gate electrode 22-2 Gate insulating film 22-3 Island 22-4 Source electrode 22-5 Drain electrode 22-6 Protective insulating film 23 Color filter layer 24 Optical anisotropic layer 25 Transparent electrode layer 26 Alignment layer 27 Through hole 28 Transfer layer 30 TFT array substrate 31 Liquid crystal 32 Counter substrate 33 Polarizing layer 34 Cellulose ester film (polarizing plate protective film)
35 Cellulose ester film or optical compensation sheet 36 Polarizing plate 37 Liquid crystal cell

Claims (16)

A method for manufacturing a substrate for a liquid crystal cell having a color filter layer, a uniaxial or biaxial optically anisotropic layer, and a TFT driving element, wherein the color filter layer and the optically anisotropic layer are transferred with a transfer material. The manufacturing method including the process provided using. The optically anisotropic layer is a layer formed by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then fixing by irradiation with heat or ionizing radiation. 2. The production method according to 1. The production method according to claim 2, wherein the ionizing radiation is polarized ultraviolet rays. The production method according to claim 1, wherein the reactive group is an ethylenically unsaturated group. The said liquid crystalline compound is a rod-shaped liquid crystal, The manufacturing method as described in any one of Claims 1-4. The said liquid crystalline compound is a disk shaped liquid crystal, The manufacturing method as described in any one of Claims 1-4. The front retardation (Re) of the optically anisotropic layer is not substantially 0, and + 40 ° with respect to the normal direction of the optically anisotropic layer with the in-plane slow axis as the tilt axis (rotation axis) The retardation value measured by making light of wavelength λ nm incident from the inclined direction, and the in-plane slow axis as the tilt axis (rotation axis), tilted by -40 ° with respect to the normal direction of the optical anisotropic layer The manufacturing method as described in any one of Claims 1-6 in which the retardation value measured by injecting the light of wavelength (lambda) nm from the measured direction is substantially equal. The optically anisotropic layer has a front retardation (Re) of 60 to 200 nm, an in-plane slow axis as an inclination axis (rotation axis), and a direction inclined by + 40 ° with respect to the normal direction of the optically anisotropic layer The production method according to claim 1, wherein the retardation value measured by making light having a wavelength of λ nm incident from 50 to 250 nm. 9. The manufacturing method according to claim 1, wherein the liquid crystal cell substrate further includes a pixel electrode, and the optically anisotropic layer is formed of the TFT more than the pixel electrode. A manufacturing method formed on the drive element side. The manufacturing method as described in any one of Claims 1-9 in which the through hole for taking the electrical connection with the said drive element is provided in the said optically anisotropic layer. The manufacturing method as described in any one of Claims 1-10 including the process of following [1]-[4] in this order:
[1] A step of transferring a transfer material having a photosensitive resin layer and an optically anisotropic layer onto a temporary support onto a TFT substrate;
[2] A step of peeling the temporary support from the transfer material on the TFT substrate;
[3] A step of pattern exposing the transfer material on the TFT substrate;
[4] A step of removing unnecessary photosensitive resin layers and optically anisotropic layers on the TFT substrate by development. The substrate for liquid crystal cells manufactured by the manufacturing method as described in any one of Claims 1-11. A liquid crystal cell substrate having a color filter layer and an optically anisotropic layer formed in the same pattern as a colored pattern of the color filter layer on a TFT substrate. A liquid crystal cell comprising the liquid crystal cell substrate according to claim 12. A liquid crystal display device comprising the liquid crystal cell according to claim 14. The liquid crystal display device according to claim 15, wherein the liquid crystal mode is either VA or IPS.

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