JP2007155898A - Method of manufacturing substrate for liquid crystal cell, substrate for liquid crystal cell and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a substrate for a liquid crystal cell with an optical anisotropic layer that contributes to improving color viewing angle characteristics of a liquid crystal display device. <P>SOLUTION: The method of manufacturing a substrate for a liquid crystal cell includes the steps of, in the following order: [1] exposing a substrate having at least one photosensitive resin layer and at least one optical anisotropic layer on a support by using a photomask to transfer a pattern: and [2] developing the substrate obtained in the step [1] by using a developer solution containing at least one kind of alkali compound and at least one kind of organic solvent having LogP of -0.5 or higher to remove an unexposed portion of the optical anisotropic layer and of the photosensitive resin layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a liquid crystal cell substrate with an optically anisotropic layer, and a liquid crystal cell substrate and a liquid crystal display device produced by using the production method, and can be used particularly for a liquid crystal display device having excellent color viewing angle characteristics. The present invention relates to a method for manufacturing a 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 OCB, VA, and IPS have wide viewing angle characteristics in all directions as wide viewing angle modes, and are already widely used in homes as television applications. A size display has also appeared.

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

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

  On the other hand, although the principle is the same as 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.

JP2004-37837A GB2394718

  An object of the present invention is to provide a method for producing a substrate for a liquid crystal cell with an optically anisotropic layer that contributes 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) At least the following steps [1] and [2]:
[1] A step of pattern-exposing a substrate having at least one photosensitive resin layer and at least one optically anisotropic layer on a support using a photomask:
[2] The substrate obtained in step [1] is developed with a developer containing at least one alkaline compound and at least one organic solvent having a Log P of −0.5 or more, and the optically anisotropic The manufacturing method of the board | substrate for liquid crystal cells which includes the process of removing the unexposed part of a photosensitive layer and a photosensitive resin layer in this order.

(2) Further, the following steps [3] to [5]:
[3] A step of producing a transfer material having at least one optically anisotropic layer and at least one photosensitive resin layer on a temporary support;
[4] Laminating the transfer material on a support;
[5] The step of separating the temporary support from the transfer material on the support to obtain a substrate having at least one photosensitive resin layer and at least one optically anisotropic layer on the support. The manufacturing method according to (1), which is included in this order before the steps [1] and [2].
(3) The production method according to (1) or (2), wherein at least one of the organic solvents is an aromatic alcohol.
(4) The manufacturing method according to any one of (1) to (3), wherein the optically anisotropic layer includes a composition containing a monomer having at least one acidic group.

(5) The optically anisotropic layer is a layer irradiated with heat or ionizing radiation after forming a liquid crystal phase by applying and drying a solution containing a liquid crystalline compound having at least one reactive group (1) The manufacturing method as described in any one of-(4).
(6) The production method according to (5), wherein the ionizing radiation is polarized ultraviolet light.
(7) The production method according to (5) or (6), wherein the reactive group is an ethylenically unsaturated group.
(8) The manufacturing method according to any one of (5) to (7), wherein the optically anisotropic layer includes a radical polymerization initiator.
(9) The production method according to any one of (5) to (8), wherein the liquid crystalline compound is a rod-like liquid crystal.
(10) The production method according to any one of (5) to (8), wherein the liquid crystalline compound is a discotic liquid crystalline compound.

(11) The manufacturing method according to any one of (5) to (10), wherein the optically anisotropic layer exhibits a cholesteric phase before being heated or irradiated with light.
(12) The production method according to any one of (1) to (11), wherein the photosensitive resin layer is formed by adding at least a radical polymerization initiator.
(13) 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 (12), wherein retardation values measured by making light having a wavelength λ nm incident from a direction inclined by 40 ° are substantially equal.

(14) The front retardation (Re) of the optically anisotropic layer is 20 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 (12), wherein retardation values measured by making light having a wavelength λ nm incident from an inclined direction are substantially equal and the values are 50 to 250 nm.
(15) A liquid crystal cell substrate produced by the production method according to any one of (1) to (14).
(16) A liquid crystal display device having the liquid crystal cell substrate according to (15).
(17) The liquid crystal display device according to (16), wherein the liquid crystal mode is either VA or IPS.

  By using the liquid crystal cell substrate manufactured by the manufacturing method of the present invention, the liquid crystal cell can be optically compensated for each color. A liquid crystal display device having a liquid crystal cell substrate manufactured by using the manufacturing method of the present invention has improved viewing angle characteristics, 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.

[Substrate for liquid crystal cell]
The liquid crystal cell substrate produced by the production method of the present invention will be described.
The substrate for a liquid crystal cell produced by the production method of the present invention can constitute an optically anisotropic layer for compensating the viewing angle of the liquid crystal cell. Furthermore, an optically anisotropic layer for compensating the viewing angle of the liquid crystal cell can be formed for each of R, G, and B colors by combination with a color filter. The substrate on which such a layer is formed may be used for one of a pair of substrates of a liquid crystal cell, or may be used by being divided into both.

  FIG. 1A shows a schematic cross-sectional view of an example of a liquid crystal cell substrate having a patterned optically anisotropic layer produced by the production method of the present invention. The substrate 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. A black matrix 22 is generally formed on a substrate, and a photosensitive resin layer formed on the substrate by various methods (coating using a coating solution or transferring using a transfer material) and then patterned by mask exposure or the like. A color filter layer 23 and a patterning optically anisotropic layer 27 are formed. FIG. 1 shows an embodiment in which the color filter layers 13 of R, G, and B are formed, but as is often seen recently, a color filter layer composed of layers of R, G, B, and W (white) is formed. May be. The optically anisotropic layer 14 is divided into r, g, and b regions, and has optimum retardation characteristics for the colors of the R, G, and B filter layers 13, respectively. A transparent electrode layer 25 is formed on the optically anisotropic layer 27, and an alignment layer 26 for aligning liquid crystal molecules in the liquid crystal cell is formed thereon.

  Furthermore, the solid optically anisotropic layer 24 which is not patterned may be provided in addition to the patterned optically anisotropic layer 27 as shown in FIG. The solid optically anisotropic layer may be made of a transfer material or may be made by another method, and the material is not particularly limited. Further, the solid optically anisotropic layer may be on the side of the liquid crystal cell substrate produced by the production method of the present invention, or may be on the side of the counter substrate although not shown. In general, a drive electrode such as a TFT array is generally arranged on the counter substrate side, and may be formed at any position on the counter substrate. However, in the case of an active drive type having a TFT, optical anisotropy is provided. The heat resistance of the conductive layer is preferably higher than that of the silicon layer.

[Transfer material]
A transfer material used when transfer is used as a method for producing the photosensitive resin layer and the optically anisotropic layer in the production method of the present invention will be described.
The transfer material has a temporary support, at least one optically anisotropic layer, and at least one photosensitive resin layer, and transfers the optically anisotropic layer and the photosensitive resin layer onto another substrate. It is a material used to do. FIG. 2 is a schematic cross-sectional view of some examples of transfer materials. The transfer material shown in FIG. 2A 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. 2B, the unevenness on the counterpart substrate side is not formed between the support 11 and the optically anisotropic layer 12 during transfer. It may have a layer 14 for controlling mechanical properties such as cushioning properties for absorbing or providing unevenness followability, and also in the optically anisotropic layer 12 as shown in FIG. A layer 15 that functions as an alignment layer for controlling the alignment of the liquid crystal molecules may be disposed, or both layers may be provided as shown in FIG. 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.2 (e).

[Liquid Crystal Display]
FIG. 3 is a schematic cross-sectional view of an example of a liquid crystal display device having the liquid crystal cell substrate of the present invention. In the example of FIGS. 3A and 3B, the liquid crystal cell substrate of FIGS. 1A and 1B is used as the upper substrate, and the liquid crystal 31 is sandwiched between the glass substrate with TFT shown in FIG. 32 as the counter substrate. This is a liquid crystal display device using the liquid crystal cell 37. On both sides of the liquid crystal cell 37, a polarizing plate 36 composed of a polarizing layer 33 sandwiched between two cellulose triacetate (TAC) films 34 and 35 is disposed. The cellulose acetate 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.

Next, each step of the production method of the present invention and materials used therein will be described in detail. The liquid crystal cell substrate produced by the production method of the present invention has a color filter layer comprising a support, a patterning optically anisotropic layer, and a photosensitive resin layer. The use of the liquid crystal cell substrate manufactured by the manufacturing method of the present invention is not particularly limited, but it is preferably used as a constituent member of a liquid crystal display device. In this aspect, the patterning optically anisotropic layer contributes to the viewing angle compensation of the cell of the liquid crystal display device, that is, the contrast viewing angle is enlarged and the image coloring of the liquid crystal display device is eliminated. When a transfer material is used in the production method of the present invention, the optically anisotropic layer and the photosensitive resin layer can be simultaneously produced on a glass substrate. As a result, the number of production steps of the liquid crystal display device is almost reduced. Without changing, the viewing angle characteristics of the liquid crystal display device, particularly the color viewing angle characteristics, can be improved.
Hereinafter, the material production method of the transfer material used when transfer is used as the production method of the photosensitive resin layer and the optically anisotropic layer in the production method of the present invention will be described in detail, but the present invention is limited to this embodiment. It is not a thing. Further, other embodiments can be prepared with reference to the following description and conventionally known methods. However, the present invention is not limited to the embodiments described below.

[Temporary support for transfer material]
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), polyolefin (eg, norbornene polymer), poly (meth) acrylic acid ester (eg, polymethyl). Methacrylate), polycarbonate, polyester and polysulfone, and norbornene-based polymers. 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 composed of a composition containing at least one acid monomer and a liquid crystal compound, and has one incident direction in which Re is not substantially 0 when the phase difference is measured. Although it is not particularly limited as long as it has optical properties that are not isotropic, it is formed from a composition containing at least one liquid crystalline compound from the viewpoint of being used in a liquid crystal cell and easily controlling optical properties. In addition, it is preferable that the liquid crystal layer containing at least one liquid crystal compound is a layer formed by being cured by irradiating with ultraviolet rays. Moreover, in order to harden | cure by ultraviolet irradiation, it is preferable to contain a radical polymerization initiator.

[Optically Anisotropic Layer Consisting of Liquid Crystalline Composition]
The optically anisotropic layer functions as an optically anisotropic layer that compensates the viewing angle of the liquid crystal display device by being incorporated in the liquid crystal cell as described above. Of course, the optically anisotropic layer alone has sufficient viewing angle compensation capability, and is required for viewing angle compensation in combination with other layers (for example, an optically anisotropic layer disposed outside the liquid crystal cell). It may be an aspect satisfying the optical characteristics. The optically anisotropic layer does not need to satisfy the optical characteristics sufficient for the optical compensation ability. For example, the optical characteristics are expressed or changed through the exposure process in the manufacturing method of the present invention. It may exhibit optical characteristics necessary for compensation.

As described above, 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 various liquid crystal cells, particularly VA mode liquid crystal cells can be accurately compensated for viewing angle. 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). Open 2002-6138). Any of them can be used in the present invention.

  When the optically anisotropic layer is uniaxial, it is preferable to optimize the optical anisotropy of either the upper or lower polarizing plate protective film because the VA mode or IPS mode liquid crystal cell can be accurately optically compensated. In both cases of the VA mode and the IPS mode, the retardation wavelength dispersion of the polarizing plate protective film is generally used to improve the color viewing angle characteristics, which is the object of the present invention. By making it smaller, the optical compensation can be made accurately over a wide wavelength range with respect to the liquid crystal cell. In the VA mode, the optically anisotropic layer as the polarizing plate protective film is preferably c-plate, and the IPS mode is preferably biaxial with the smallest refractive index in the thickness direction. The uniaxial optically anisotropic layer used in the transfer material of the present invention can be produced by aligning a uniaxial rod-like or disc-like liquid crystalline compound so that the directors of the liquid crystal are aligned in one direction. Such uniaxial alignment includes a method of aligning a non-chiral liquid crystal layer on a rubbing alignment layer or photo-alignment layer, a method of aligning with a magnetic field or an electric field, a method of aligning by applying an external force such as stretching or shearing, etc. Can be realized.

  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. 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 support are parallel, and in the case of a disc-like liquid crystal, the disc surface of the core of the disc-like liquid crystal compound. And the horizontal plane of the transparent support is parallel, but it is not required to be strictly parallel, and in this specification, an inclination angle with the horizontal plane is less than 10 degrees. To do. In the present specification, when referred to as “horizontal orientation”, 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.

  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.

[Monomer having an acidic group]
The above-described monomer having an acidic group is not particularly limited as long as it is a compound having one or more acidic groups in one molecule, but typical examples include a carboxyl group, a sulfonic acid group, (Meth) acrylic acid having a phosphoric acid group, maleic acid, styrene sulfonic acid, itaconic acid, and general formula (1):
_{CH 2 = CR 102 -COO (CH} 2) n -L-X (1)
(In the general formula (1), R ₁₀₂ is H or CH _3, n is an integer of from 1 to 10, L is a divalent linking group, X represents a carboxyl group or a sulfo group.)
The compound etc. which are represented by these are mentioned.
The divalent linking group represented by L is preferably an arylene group (an arylene group having 6 to 20 carbon atoms such as 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4 ′. - biphenylene, 1,4-naphthylene, 1,5-naphthylene and the like), - O -, - S -, - CO 2 -, - OCO -, - (CH 2) m - (m is 1 to 10 And a group formed by combining two or more groups selected from these. As the arylene group, 1,4-phenylene, 1,3-phenylene or 4,4′-biphenylene is preferable, and 1,4-phenylene is more preferable.

As a monomer represented by General formula (1), the monomer represented by following General formula (2) is mentioned as a preferable example, for example.
General formula (2):
_{CH 2 = CR 102 -COO (CH} 2) n -O-Ar- (L 1 -Ar) k -X (2)
In the general formula (2), R ₁₀₂ represents H or CH ₃ , L ₁ represents —O—, —S—, —CO ₂ — or —OCO—, n represents an integer of 1 to 10, k Represents an integer of 0 to 3, Ar represents a 1,4-phenylene group, and X represents a carboxyl group or a sulfo group. In the general formula (2), L ₁ is preferably —CO ₂ — or —OCO—, and k is preferably 1 or 2.
Specific preferred examples of the monomer having an acidic group are listed below, but the invention is not limited thereto.

Monomers having an acidic group may be used alone or in combination of two or more.
The content of these monomers in the liquid crystalline composition is not particularly limited as long as the liquid crystallinity of the liquid crystalline composition does not disappear, but from the viewpoint of developability and film physical properties, 1 mol% to 50%. The mol%, preferably 5 mol% to 30 mol%, more preferably 10 mol% to 20 mol%. (However, mol% is the content in the total monomer.)

[Fixation of alignment state of liquid crystalline composition]
The aligned liquid crystalline composition 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 an optically anisotropic layer exhibiting in-plane retardation generated by photo-alignment by polarized light irradiation is particularly excellent for compensating the viewing angle of a VA mode liquid crystal display device.

[Optical alignment by polarized irradiation]
The 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. In the present invention, 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.

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

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

式中、Ｒ¹、Ｒ²及びＲ³は各々独立して、水素原子又は置換基を表し、Ｘ¹、Ｘ²及びＸ³は単結合又は二価の連結基を表す。Ｒ¹〜Ｒ³で各々表される置換基としては、好ましくは置換もしくは無置換の、アルキル基（中でも、無置換のアルキル基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及びＸ³で各々表される二価の連結基は、アルキレン基、アルケニレン基、二価の芳香族基、二価のヘテロ環残基、−ＣＯ−、―ＮＲ^a−（Ｒ^aは炭素原子数が１〜５のアルキル基または水素原子）、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−及びそれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。二価の連結基は、アルキレン基、フェニレン基、−ＣＯ−、−ＮＲ^a−、−Ｏ−、−Ｓ−及び−ＳＯ₂−からなる群より選ばれる二価の連結基又は該群より選ばれる基を少なくとも二つ組み合わせた二価の連結基であることがより好ましい。アルキレン基の炭素原子数は、１〜１２であることが好ましい。アルケニレン基の炭素原子数は、２〜１２であることが好ましい。二価の芳香族基の炭素原子数は、６〜１０であることが好ましい

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

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

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each preferably a substituent represented by R ¹ , R ² and R ³ in the general formula (I). It is listed as a thing. As the horizontal alignment agent used in the present invention, the compounds described in JP-A-2005-99248 can be used, and the synthesis method of these compounds is also described in the specification.

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

[Alignment layer]
As described above, an alignment layer may be used to form the optically anisotropic layer. The alignment layer is generally provided on a transparent support or an undercoat layer coated on the transparent support. The alignment layer functions so as to define the alignment direction of the liquid crystal compound provided thereon. The orientation layer may be any layer as long as it can impart orientation to the optically anisotropic layer. Preferred examples of the alignment layer include a layer subjected to a rubbing treatment of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, and ω-tricosanoic acid, dioctadecylmethylammonium chloride and stearyl Examples thereof include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field. The alignment layer may have a function as an oxygen blocking layer.

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

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

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

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

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.

[Photosensitive resin layer]
The photosensitive resin layer is made of a photosensitive resin composition and may be positive or negative as long as there is a difference in adhesion to the substrate between the exposed and unexposed areas when irradiated through a photomask or the like. There is no particular limitation. 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 preferably formed from a colored resin composition containing
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.
The alkali-soluble resin used for the photosensitive resin layer is particularly preferably one that is soluble in an organic solvent.

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

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

(3) Photopolymerization initiator or photopolymerization initiator system The photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer of the present invention is disclosed in US Pat. No. 2,367,660. Vicinal polyketaldonyl 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. Nos. 3046127 and 2951758, a combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, and Japanese Patent Publication No. 51-48516. Benzothiazole compounds and trihalomethyl-s-triazine compounds described, US Pat. No. 4,239,850 Trihalomethyl described in the specification - 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 diameter is preferably 0.1 μm or less, particularly preferably 0.08 μm or less. .
Examples of the known dye or pigment include pigments described in paragraph No. [0033] of JP-A No. 2004-302015 and column 14 of US Pat. No. 6,790,568.

  As the colorant in the present invention, among the above-mentioned colorants, (i) R (red) colored resin composition is C.I. I. Pigment Red 254 is C.I. in (ii) G (green) colored resin composition. I. Pigment Green 36 is C.I. in (iii) B (blue) colored resin composition. 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 the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

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

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

  The contrast of each colored pixel of the color filter formed from the photosensitive resin layer is preferably 2000 or more, more preferably 2800 or more, still more preferably 3000 or more, and most preferably 3400 or more. When the contrast of each colored pixel constituting the color filter is 2000 or less, when an image of a liquid crystal display device having the color pixel is observed, an overall whitish impression is obtained, which is not preferable. Further, the difference in contrast between the colored pixels is preferably within 600, more preferably within 410, still more preferably within 350, and most preferably within 200. 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 the color filter layer formed by the photosensitive resin layer of the transfer material, an appropriate surfactant is added to the colored resin composition from the viewpoint of effectively preventing display unevenness (color unevenness due to film thickness variation). It is preferable to contain. The surfactant can be used as long as it is mixed with the photosensitive resin composition. Preferred surfactants used in the present invention include JP2003-337424A [0090] to [0091], JP2003-177522A [0092] to [0093], and JP2003-177523A [0094]. ] To [0095], JP 2003-177521 A [0096] to [0097], JP 2003-177519 A [0098] to [0099], JP 2003-177520 A [0100] to [0101]. [0102] to [0103] of JP-A-11-133600 and surfactants disclosed as inventions of JP-A-6-16684 are preferred. In order to obtain a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) ) Or two or more types are preferable, and a fluorine-based surfactant is most preferable. When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. If the number of fluorine atoms is too large, it is not preferable in that the solubility in an ordinary solvent not containing fluorine is lowered. When the number of fluorine atoms is too small, it is not preferable in that the effect of improving unevenness cannot be obtained.

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

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

A particularly preferred surfactant represented by the general formula (a) is referred to as a monomer (a), and a monomer represented by the general formula (b) is referred to as a monomer (b). C _m F _{2m + 1} shown in the general formula (a) may be linear or branched. m shows the integer of 2-14, Preferably it is an integer of 4-12. The content of C _m F _{2m + 1} is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass, based on the monomer (a). R ₁ represents a hydrogen atom or a methyl group. Moreover, n shows 1-18, and 2-10 are preferable especially. R ₂ and R ₃ shown in the general formula (b) each independently represent a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p and q each represents an integer of 0 to 18, but neither p nor q contains 0. p and q are preferably 2 to 8.

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

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

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

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

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

  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 Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants, or silicon-based surfactants Can be mentioned. 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]
Between the support and the optically anisotropic layer in the transfer material, between the thermoplastic resin layer for controlling the mechanical properties and unevenness followability of the transfer material, and during and after the application of multiple coating layers An intermediate layer for preventing mixing of components during storage may be provided. As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

  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 in 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.

  The optically anisotropic layer and the photosensitive resin layer, and the orientation layer, the thermoplastic resin layer, and the intermediate layer, which are formed as required, are dip coat method, air knife coat method, curtain coat method, roller coat method, wire bar. It can be formed by coating by a coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). Two or more layers may be applied simultaneously. The 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 optically anisotropic layer using transfer material]
The method for transferring the transfer material onto the support 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 support. For example, the transfer material formed in a film shape 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 layer side 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 the support for transferring the transfer material, for example, a transparent support is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, or the like, A plastic film etc. can be mentioned. The transfer material to which the transfer material is transferred may be a material provided with a layer such as a solid optically anisotropic layer on a support. In addition, the material to be transferred such as the support can have good adhesion to the photosensitive resin layer by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

[exposure]
In the method for producing a substrate for a liquid crystal cell of the present invention, in order to obtain a photosensitive resin layer and an optically anisotropic layer having an arbitrary pattern, the substrate for a liquid crystal display device having both is exposed. A predetermined mask is disposed between the substrate and the exposure light source, and then exposure is performed through the mask. 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. Energy of exposure generally 1mJ / cm ² ~10J / cm ² or so, preferably from 5mJ / cm ² ~5J / cm ² or so, particularly preferably 10~200mJ / cm ² approximately. In the present invention, since the adhesion strength between the layers changes only in the exposed portion at the time of exposure, development by a peeling operation becomes possible later.

[developing]
Next, development is performed. In this specification, “development” means a step of removing unnecessary photosensitive resin layers and optically anisotropic layers on a substrate. By this step, a desired pattern can be obtained for the photosensitive resin layer and the optically anisotropic layer. By development, an R color pattern is formed in which a specific colored resin layer, for example, a laminate of a red (R) resin layer and an optically anisotropic layer is disposed on a substrate at a predetermined position. A patterned optically anisotropic layer formed in the same pattern as the color filter and its 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 substrate for a liquid crystal cell having

[Developer]
The developer used in the production method of the present invention is characterized by containing at least one alkaline compound and at least one organic solvent having a Log P of −0.5 or more. Here, LogP is a parameter representing hydrophobicity / hydrophilicity, and is a parameter that can be obtained from the distribution coefficient of substances in two solvent systems, usually in n-octanol and water. The method of obtaining the parameters is described in detail in Chemistry Special Issue No. 122 “Drug Structure-Activity Relationship” (Nan-Edo) p73-103. In recent years, various software for calculating LogP has been proposed, and LogP in this specification is a value calculated using “CS ChemDraw Pro 6.0” (Cambridgesoft). The LogP is preferably −0.5 or more, more preferably LogP is 0.5 or more.

  By containing an organic solvent having Log P of −0.5 or more, the permeability to the optically anisotropic layer is improved and the photosensitive resin layer in the unexposed area is dissolved. Examples of organic solvents having a Log P of −0.5 or more include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n— Alcohols such as butyl ether, benzyl alcohol, phenethyl alcohol, 2-phenoxyethanol, 2-phenoxyethoxyethanol, ethylene glycol monobenzyl ether, 1-phenoxypropanol, 1-phenoxy-2-propanol, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketones, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, ethyl lactate, butyl lactate, ethylene glycol monomethyl acetate Tate, ethylene glycol monoethyl acetate, esters such as γ-butyrolactone, dimethylacetamide, diethylacetamide, amides such as N-methylpyrrolidone, N-methylpyrrolidone, 1,4-dioxane, ethers such as tetrahydrofuran And a mixture of two or more selected from the group consisting of acetonitrile and the like. Among these, a solvent containing at least one kind of alcohol solvent is preferable, and a solvent containing at least one kind of aromatic alcohol is more preferable. The developer used in the production method of the present invention is particularly preferably a mixed solution of the above organic solvent and water, and is a mixed solution with a known developer such as that described in JP-A-5-72724. It is also preferable. In addition, since a developing solution melt | dissolves the photosensitive resin layer, it is preferable to contain an alkaline compound, for example, what contains the compound of pka = 7-13 in the density | concentration of 0.05-5 mol / L is preferable. In the case of a mixture of an organic solvent and water, the concentration of the organic solvent is preferably 0.5% by mass to 90% by mass, particularly preferably 1% by mass to 50% by mass, and 1.5% by mass to 30% by mass. % Is most preferred. 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. Moreover, you may add antifoaming agents, such as silicone oil and a polyalkylene derivative, chelating agents, such as EDTA, an inorganic builder.

Although it does not specifically limit as an alkaline compound contained in a developing solution, Both an inorganic alkaline compound and an organic alkaline compound can be used. Inorganic alkaline compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid diphosphate. Examples include potassium hydrogen, sodium dihydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia. Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopyramine, diisopyramine, monoethanolamine, N- Examples include methylaminomethanol, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibutylaminoethanol, N-methyl-N- (2-hydroxyethyl) aminoethanol, diethanolamine, and triethanolamine. .
Of these, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, trimethylethylammonium hydroxide and the like are preferable.

  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 split alignment protrusions 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 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.20
MegaFuck F-780-F (Dainippon Ink Chemical Co., Ltd.)
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-R1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as the coating liquid LC-R1 for the optically anisotropic layer.
LC-1-1 was obtained from Tetrahedron Lett. 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)
22.02
Chiral agent (Paliocolor LC756, BASF Japan)
3.40
4,4′-Azoxydianisole 0.52
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 3.30
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COOH 3.30
(However, Ph represents a phenylene group)
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.36
Methyl ethyl ketone 66.0
────────────────────────────────

(Preparation of coating liquid LC-G1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-G1 for an optically anisotropic layer.
────────────────────────────────
Coating composition for optically anisotropic layer (%)
────────────────────────────────
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan)
21.78
Chiral agent (Paliocolor LC756, BASF Japan)
3.34
4,4′-Azoxydianisole 0.27
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 3.30
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COOH 3.30
(However, Ph represents a phenylene group)
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.34
Methyl ethyl ketone 66.57
────────────────────────────────

(Preparation of coating liquid LC-B1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-B1 for an optically anisotropic layer.
────────────────────────────────
Coating composition for optically anisotropic layer (%)
────────────────────────────────
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan)
22.12
Chiral agent (Paliocolor LC756, BASF Japan)
3.36
4,4′-Azoxydianisole 0.03
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 3.30
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COOH 3.30
(However, Ph represents a phenylene group)
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.34
Methyl ethyl ketone 66.45
────────────────────────────────

(Preparation of coating liquid LC-R2 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-R2 for an optically anisotropic layer.
────────────────────────────────
Coating composition for optically anisotropic layer (%)
────────────────────────────────
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan)
28.62
Chiral agent (Paliocolor LC756, BASF Japan)
3.40
4,4′-Azoxydianisole 0.52
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.36
Methyl ethyl ketone 66.0
────────────────────────────────

(Preparation of coating liquid LC-G2 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as the coating liquid LC-G2 for the optically anisotropic layer.
────────────────────────────────
Coating composition for optically anisotropic layer (%)
────────────────────────────────
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan)
28.38
Chiral agent (Paliocolor LC756, BASF Japan)
3.34
4,4′-Azoxydianisole 0.27
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.34
Methyl ethyl ketone 66.57
────────────────────────────────

(Preparation of coating liquid LC-B2 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-B2 for an optically anisotropic layer.
────────────────────────────────
Coating composition for optically anisotropic layer (%)
────────────────────────────────
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan)
28.72
Chiral agent (Paliocolor LC756, BASF Japan)
3.36
4,4′-Azoxydianisole 0.03
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.34
Methyl ethyl ketone 66.45
────────────────────────────────
────────────────────────────────

Below, the preparation methods of the coating liquid for colored photosensitive resin layers are demonstrated. 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 =
38/25/37 molar ratio random copolymer (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 =
Random copolymer of 36/22/42 molar ratio (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 liquid PP-K1 for the photosensitive resin layer is first weighed in the amount of K pigment dispersion 1 and propylene glycol monomethyl ether acetate shown in Table 2, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred 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 in the amounts shown in Table 2 -Bromophenyl] -s-triazine and Megafac F-176PF are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. It was.

(Preparation of coating solution PP-R1 for photosensitive resin layer)
The coating solution PP-R1 for the photosensitive resin layer first weighs the R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 2 at a temperature of 24 ° C. (± 2 ° C.). Mix and stir at 150 rpm for 10 minutes, then the amount of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole listed in Table 2 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine were weighed, and the temperature was 24 ° C. (± 2 ° C.). And then stirred at 150 rpm for 10 minutes, and then weighed out the amount of ED152 shown in Table 2 and mixed at a temperature of 24 ° C. (± 2 ° C.). Further, the amount of Megafac F-176PF shown in Table 2 was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 30 minutes, and filtered through nylon mesh # 200. It was.

(Preparation of coating solution PP-G1 for photosensitive resin layer)
The coating solution PP-G1 for the photosensitive resin layer is prepared by first weighing out the G pigment dispersion, CF yellow EX3393, and propylene glycol monomethyl ether acetate in the amounts shown in Table 2, and mixing them 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, 4-Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine are weighed in this order at a temperature of 24 ° C. (± 2 ° C.). Add and stir at 150 rpm for 30 minutes, then weigh out the amount of MegaFac F-176PF listed in Table 2 and set the temperature at 24 ° C. It was obtained by adding (± 2 ° C.), stirring at 30 rpm for 5 minutes, and filtering through 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 2, 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 2, They were added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 rpm for 30 minutes. It was obtained by adding (± 2 ° C.), stirring at 30 rpm for 5 minutes, and filtering through nylon mesh # 200.

(Preparation of photosensitive resin transfer material for black matrix)
A thermoplastic resin layer coating solution CU-1 was applied and dried on a 75 μm thick polyethylene terephthalate film temporary support using a slit nozzle. Next, the intermediate layer coating solution AL-1 was applied and dried. Furthermore, the photosensitive resin composition PP-K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.4 μm was provided, and a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded. In this way, a photosensitive resin transfer material K-1 for black matrix in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

(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 .

(Preparation of RGB optical anisotropic layer transfer material containing acidic groups)
A thermoplastic resin layer coating solution CU-1 was applied and dried on a 75 μm thick polyethylene terephthalate film temporary support using a slit nozzle. Next, the alignment layer coating liquid AL-1 was applied and dried. The film thickness of the thermoplastic resin layer was 14.6 μm, and the alignment layer was 1.6 μm. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-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 in a nitrogen atmosphere with an oxygen concentration of 0.3% or less using POLUV-1 so that the transmission axis of the polarizing plate was in the TD direction of the temporary support. (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 was spin-coated so as to have a film thickness of 2.0 μm and dried to prepare an R transfer material R-1.
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, transfer materials G-1 and B-1 for G and B were formed. The optically anisotropic layers of G-1 and B-1 were 2.75 μm and 2.3 μm, respectively.

(Preparation of optically anisotropic layer transfer material for RGB that does not contain acidic groups)
Transfer materials R-2, G-2, and B-2 were prepared in the same manner except that LC-R2, LC-G2, and LC-B2 were used instead of LC-R1, LC-G1, and LC-B1, respectively. did.
(Preparation of RGB transfer material without optically anisotropic layer)
The transfer material R-3, except that the photosensitive resin composition PP-R1, PP-G1, PP-B1 was coated on the temporary support without coating with the coating liquid for the optically anisotropic layer. G-3 and B-3 were produced.

(Phase difference measurement)
Retardation Re (40) when the sample is tilted by ± 40 degrees with the front retardation Re (0) at the arbitrary wavelength λ and the slow axis as the rotation axis by the parallel Nicol method using a fiber type spectrometer. (-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 2 shows the phase difference measurement results.

(Preparation of liquid crystal cell substrate of Example 1)
A color filter was produced by the following method.
-Formation of black (K) image-
The alkali-free glass substrate to be the support is washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after pure water shower washing, a silane coupling solution (N-β (Aminoethyl) γ-aminopropyltrimethoxysilane 0.3% aqueous solution, trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
After peeling off the protective film of the photosensitive resin transfer material K-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries (Lamic II type)), a rubber roller temperature of 130 ° C. Lamination was performed at a linear pressure of 100 N / cm and a conveying speed of 2.2 m / min.
After peeling the temporary support, the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp. The distance between the surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² .
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, 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.
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, stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) with a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a shower and a rotating brush having nylon bristles to obtain an image of black (K), and then further from the side of the resin layer to the substrate with an ultrahigh pressure mercury lamp at a light of 500 mJ / cm ² . After post exposure, heat treatment was performed at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Formation of red (R) image-
After the protective film of the photosensitive resin transfer material R-1 was peeled off, a black (K) image heated at 100 ° C. for 2 minutes was formed using a laminator (manufactured by Hitachi Industries (Lamic II type)). The substrate was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After peeling off the temporary support, the exposure mask 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 distance between the surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 65 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 alignment layer.
Subsequently, an aqueous solution containing 2.38% tetramethylammonium hydroxide as an alkaline compound and 50% methanol of logP = −0.27 as an organic solvent was used as a developer, and a shower was performed at 30 ° C. with a cone nozzle pressure of 0.15 MPa. While developing, the development residue on the surface was removed with a rotating brush. In this step, the optically anisotropic layer and the photosensitive resin layer were developed to obtain a patterned pixel. At this time, the developability was evaluated by measuring the time until the unnecessary photosensitive resin layer and optically anisotropic layer could be removed.
Continuing with detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)), 33 ° C., 20 seconds, cone type nozzle Residue removal was performed with a rotating brush having a shower and nylon bristles at a pressure of 0.02 MPa to obtain a red (R) image, and then further to the substrate from the resin layer side with an ultrahigh pressure mercury lamp at 500 mJ / After post-exposure with cm ² light, heat treatment was performed at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Green (G) image formation-
Using the photosensitive resin transfer material G-1, a green (G) pixel was obtained on the substrate on which the red (R) pixel was formed in the same process as the photosensitive resin transfer material R-1. However, the exposure amount was 50 mJ / cm ² . The substrate on which the R and G images were formed was again washed 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 blue (B) image-
Using the photosensitive resin transfer material B-1, blue (B) is formed on the substrate on which the red (R) pixels and green (G) pixels are formed in the same process as the photosensitive resin transfer material R-1. Obtained pixels. However, the exposure amount was 85 mJ / cm ² . The substrate on which the R, G, and B pixels are formed is again cleaned with a brush as described above, and after pure water shower cleaning, the substrate is heated at 100 ° C. for 2 minutes without using a silane coupling solution. did. The substrate on which the R, G, B, and K images were formed was baked at 240 ° C. for 50 minutes to produce a liquid crystal cell substrate of Example 1.

(Preparation of substrate for liquid crystal cell of Example 2)
Instead of the developer used in Example 1, an aqueous solution containing 2.38% tetramethylammonium hydroxide as an alkaline compound and 2-propanol with logP = 0.36 as an organic solvent was used as the developer. A liquid crystal cell substrate was produced in the same manner as in Example 1.
(Preparation of substrate for liquid crystal cell of Example 3)
Instead of the developer used in Example 1, an aqueous solution containing 2.38% tetramethylammonium hydroxide as an alkaline compound and 2.5% benzyl alcohol with log P = 1.16 as an organic solvent was used as the developer. A liquid crystal cell substrate was produced in the same manner as in Example 1 except that.

(Preparation of substrate for liquid crystal cell of Example 4)
Instead of the developer used in Example 1, an aqueous solution containing 2.38% tetramethylammonium hydroxide as an alkaline compound and 2.5% 2-phenoxyethanol with logP = 1.18 as an organic solvent was used as the developer. A liquid crystal cell substrate was produced in the same manner as in Example 1 except that it was used.
(Preparation of substrate for liquid crystal cell of Example 5)
Instead of the developer used in Example 4, an aqueous solution containing 1.5% potassium hydroxide as the alkaline compound and 2.5% 2-phenoxyethanol with logP = 1.18 as the organic solvent was used as the developer. Produced a liquid crystal cell substrate in the same manner as in Example 4.

(Preparation of substrate for liquid crystal cell of Reference Example 1)
Instead of the developer used in Example 1, an aqueous solution containing 2.38% tetramethylammonium hydroxide as an alkaline compound and 1,3-propanediol having log P = −0.61 as an organic solvent was used as the developer. A liquid crystal cell substrate was produced in the same manner as in Example 1 except that.
(Preparation of substrate for liquid crystal cell of Reference Example 2)
A substrate for a liquid crystal cell was produced in the same manner as in Example 1 except that a 2.38% tetramethylammonium hydroxide aqueous solution was used as the developer instead of the developer used in Example 1.

(Preparation of substrate for liquid crystal cell of Example 6)
R-1, G-1, and B-1 are changed to R-2, G-2, and B-2, and red (R), green (G), and blue (B) images are formed as alkaline compounds. Shower development using an aqueous solution containing 38% tetramethylammonium hydroxide and 2.5% 2-phenoxyethanol with logP = 1.18 as an organic solvent at 50 ° C. and a cone type nozzle pressure of 0.15 MPa A liquid crystal cell substrate was produced in the same manner as in Example 4.
(Reference Example 3: Production of color filter)
A substrate for a liquid crystal cell was produced in the same manner as in Example 6 except that a 2.38% tetramethylammonium hydroxide aqueous solution was used as the developer instead of the developer used in Example 6.
Table 3 shows the results of evaluation of developability.

  As shown in Table 4, in the step of removing the unnecessary photosensitive resin layer and the optically anisotropic layer on the substrate, a developer containing at least one alkaline compound and an organic solvent having a log P of −0.5 or more It can be seen that the development speed is increased by using. Further, when the optically anisotropic layer is a liquid crystalline composition containing a monomer having an acidic group, the development speed is remarkably increased, and the productivity of the liquid crystal cell substrate can be improved.

(Production of color filter without optically anisotropic layer)
In Example 1, instead of the transfer materials R-1, G-1, and B-1, photosensitive resin transfer materials R-3, G-3, and B-3 having no optically anisotropic layer were used. Unnecessary development of the photosensitive resin layer is carried out by using a sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, Example 1 except that a patterning pixel was obtained by using a stabilizer containing, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd., and performing shower development at a cone type nozzle pressure of 0.15 MPa to remove the photosensitive resin layer. A liquid crystal cell substrate was prepared in the same manner as described above.

(Formation of transparent electrode)
A transparent electrode film was formed by sputtering ITO on the liquid crystal cell substrate prepared in the above example.

(Preparation of photosensitive transfer material for protrusions)
A thermoplastic resin layer coating solution CU-1 was applied on a 75 μm thick polyethylene terephthalate film temporary support and dried to provide a thermoplastic resin layer having a dry film thickness of 15 μm.
Next, the intermediate layer / alignment layer coating solution AL-1 was applied on the thermoplastic resin layer and dried to provide an intermediate layer having a dry film thickness of 1.6 μm.
On the said intermediate | middle layer, the coating liquid which consists of the following prescription was apply | coated and dried, and the photosensitive resin layer for liquid crystal orientation control protrusions with a dry film thickness of 2.0 micrometers was provided.
────────────────────────────────
Protrusion coating composition (%)
────────────────────────────────
FH-2413F (manufactured by FUJIFILM Arch Corporation) 53.3
Methyl ethyl ketone 46.7
Mega Fuck F-176PF 0.04
────────────────────────────────
Further, a 12 μm-thick polypropylene film is attached to the surface of the photosensitive resin layer as a cover film, and a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a cover film are laminated in this order on the temporary support. A transfer material was prepared.

(Forming protrusions)
The cover film is peeled off from the projection transfer material produced above, and the surface of the photosensitive resin layer and the surface of the color filter side substrate on which the ITO film is provided are overlapped to form a laminator (Hitachi Industry Co., Ltd.). Using a product made by Izu (Lamic II type), bonding was performed under the conditions of a linear pressure of 100 N / cm, a temperature of 130 ° C., and a conveying speed of 2.2 m / min. Thereafter, only the temporary support of the transfer material was peeled and removed at the interface with the thermoplastic resin layer. In this state, the photosensitive resin layer, the intermediate layer, and the thermoplastic resin layer are laminated in this order on the color filter side substrate.
Next, a proximity exposure machine is disposed above the outermost thermoplastic resin layer so that the photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and an ultrahigh pressure mercury lamp is passed through the photomask. Proximity exposure was performed at an irradiation energy of 70 mJ / cm 2. Thereafter, a 1% triethanolamine aqueous solution was sprayed onto the substrate at 30 ° C. for 30 seconds with a shower type developing device to dissolve and remove the thermoplastic resin layer and the intermediate layer. At this stage, the photosensitive resin layer was not substantially developed.
Subsequently, 0.085 mol / L sodium carbonate, 0.085 mol / L sodium hydrogen carbonate, and 1% sodium dibutylnaphthalenesulfonate aqueous solution were developed while spraying onto the substrate at 33 ° C. for 30 seconds using a shower type developing device. Then, unnecessary portions (uncured portions) of the photosensitive resin layer were developed and removed. Then, protrusions made of a photosensitive resin layer patterned in a desired shape were formed on the base of the spacer formed by laminating the red (R) and green (G) patterns and on the color filter side substrate. . Next, the color filter side substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes, so that the green (G) is formed on the base of the spacer formed by stacking the red (R) and the green (G). A liquid crystal alignment control protrusion having a height of 1.5 μm and a vertical cross-sectional shape could be formed on the spacer having a height of 3.0 μm from the pixel and the color filter side substrate.

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

(Example 7: Production of VA-LCD)
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 this backlight, and a VA-LCD of Example 7 was produced.

(Comparative Example 1: Production of VA-LCD)
Instead of the color filter used in Example 7, a color filter without an optically anisotropic layer was used. On the protective film on the liquid crystal cell side of the lower polarizing plate, AL-1 and LC-G1 were used to obtain G-1. A VA-LCD of Comparative Example 1 was produced in the same manner as in Example 7 except that a 2.75 μm optical anisotropic layer was formed by the same method as that for producing the optically anisotropic layer.

(Evaluation of VA-LCD)
The viewing angle characteristics of the manufactured liquid crystal display device were measured with a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM). About Example 7 and Comparative Example 1 on the xy chromaticity diagram when the viewing angle is changed by 0 to 80 degrees in the right direction, upper right 45 degrees direction, and upward direction from the front of the LCD in black display (no voltage applied) FIG. 4 shows the color change in FIG.

It is a schematic sectional drawing of an example of the board | substrate for liquid crystal cells produced with the manufacturing method of this invention. 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 liquid crystal display device which has the board | substrate for liquid crystal cells produced with the manufacturing method of this invention. It is a figure which shows the color viewing angle characteristic of VA-LCD produced in Example 7 and Comparative Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Temporary support 12 Optical anisotropic layer 13 Photosensitive resin layer 14 Mechanical property control layer 15 Orientation control layer 16 Protective layer 21 Transfer substrate 22 Black matrix 23 Color filter layer 24 Solid optical anisotropic layer 25 Transparent electrode layer 26 Alignment layer 27 Patterning optical anisotropic layer 31 Liquid crystal 32 TFT
33 Polarizing layer 34 Cellulose acetate film (polarizing plate protective film)
35 Cellulose acetate film or optical compensation sheet 36 Polarizing plate 37 Liquid crystal cell

Claims (17)

At least the following steps [1] and [2]:
[1] A step of pattern-exposing a substrate having at least one photosensitive resin layer and at least one optically anisotropic layer on a support using a photomask:
[2] The substrate obtained in step [1] is developed with a developer containing at least one alkaline compound and at least one organic solvent having a Log P of −0.5 or more, and the optically anisotropic The manufacturing method of the board | substrate for liquid crystal cells which includes the process of removing the unexposed part of a photosensitive layer and a photosensitive resin layer in this order. Furthermore, the following steps [3] to [5]:
[3] A step of producing a transfer material having at least one optically anisotropic layer and at least one photosensitive resin layer on a temporary support;
[4] Laminating the transfer material on a support;
[5] separating the temporary support from the transfer material on the support to obtain a substrate having at least one photosensitive resin layer and at least one optically anisotropic layer on the support; The manufacturing method of Claim 1 included in this order before the process of process [1] and [2]. The production method according to claim 1, wherein at least one of the organic solvents is an aromatic alcohol. The manufacturing method according to claim 1, wherein the optically anisotropic layer is made of a composition containing a monomer having at least one acidic group. The optically anisotropic layer is a layer irradiated with heat or ionizing radiation after coating and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase. The manufacturing method as described in any one. The manufacturing method according to claim 5, wherein the ionizing radiation is polarized ultraviolet rays. The production method according to claim 5 or 6, wherein the reactive group is an ethylenically unsaturated group. The manufacturing method as described in any one of Claims 5-7 in which the said optically anisotropic layer contains a radical polymerization initiator. The manufacturing method according to claim 5, wherein the liquid crystal compound is a rod-like liquid crystal. The manufacturing method according to claim 5, wherein the liquid crystal compound is a discotic liquid crystal compound. The manufacturing method according to any one of claims 5 to 10, wherein the optically anisotropic layer exhibits a cholesteric phase before being heated or irradiated with light. The manufacturing method according to claim 1, wherein the photosensitive resin layer is formed by adding at least a radical polymerization initiator. 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 1-12 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 20 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 13. The method according to claim 1, wherein the retardation values measured by making light having a wavelength of λ nm incident are substantially equal, and the values are 50 to 250 nm. The liquid crystal cell substrate manufactured by the manufacturing method as described in any one of Claims 1-14. A liquid crystal display device comprising the liquid crystal cell substrate according to claim 15. The liquid crystal display device according to claim 16, wherein the liquid crystal mode is either VA or IPS.

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