JP2007264627A - Laminated structure, method of producing liquid crystal cell substrate using the same, liquid crystal cell substrate, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated structure useful for forming an optically anisotropic layer inside of a liquid crystal cell and to provide the laminated structure especially useful for forming a liquid crystal cell substrate with the optically anisotropic layer having an optically compensating ability inside of a liquid crystal cell. <P>SOLUTION: The laminated structure comprises at least one optically anisotropic layer formed of a liquid crystalline composition comprising a compound having two or more types of reactive groups, and at least one photosensitive resin layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminated structure having an optically anisotropic layer and a photosensitive resin layer, a method for producing a liquid crystal cell substrate using the laminated structure as a transfer material, a liquid crystal cell substrate, and a liquid crystal display device.

  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.

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

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

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

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

JP 2004-37837 A GB2394718 Japanese Patent Laying-Open No. 2005-4124 JP 2005-24919 A JP 2005-24920 A

  The present invention provides a laminated structure useful for forming an optically anisotropic layer in a liquid crystal cell, and in particular, a substrate for a liquid crystal cell with an optically anisotropic layer having optical compensation capability in the liquid crystal cell. It is an object of the present invention to provide a laminated structure that is useful for manufacturing the structure. Another object of the present invention is to provide a liquid crystal cell substrate having a patterned optically anisotropic layer, and a simple method for producing the liquid crystal cell substrate. The present invention also provides a novel liquid crystal cell substrate having a wide viewing angle widening performance when applied to an image display device, and a liquid crystal having a patterned optically anisotropic layer. It is an object to provide a cell substrate. It is another object of the present invention to provide a liquid crystal display device in which the liquid crystal cell is accurately optically compensated, has excellent productivity, and has improved color viewing angle characteristics.

Means for solving the above problems are as follows.
(1) A laminated structure having at least one optically anisotropic layer made of a liquid crystalline composition containing a compound having two or more reactive groups and at least one photosensitive resin layer.
(2) The two or more reactive groups are two or more selected from the group consisting of a (meth) acryloyl group, an oxetanyl group, an epoxy group, an alkoxysilyl group, an allyl group, an acrylamide group, and a vinyloxycarbonyl group. The laminated structure according to (1), which is a group of
(3) The compound is represented by the following general formula (11):

（式中、Ｒ₁₀₂は水素原子またはメチル基を表し、Ｒ₂は水素原子、メチル基またはエチル基を表し、ＳＰ１およびＳＰ２は、それぞれ独立して、単結合、直鎖もしくは分岐アルキレン基、または２以上の直鎖もしくは分岐アルキレン基が−Ｏ−、−Ｃ≡Ｃ−および−Ｓ−からなる群から選択される基によって連結されてなる基を表し、Ｌ１およびＬ２はそれぞれ２価の連結基を表し、Ｍはメソゲン基を表す。）
で表される化合物からなる群から選択される（１）に記載の積層構造体。
（４）ＳＰ１が -（ＣＨ₂）_m- で表される基であり、かつＳＰ２が-（ＣＨ₂）_n- で表される基である（ただし、ｍおよびｎはそれぞれ０〜１０の整数を表す）（３）に記載に記載の積層構造体。
（５）ＳＰ２が -（ＣＨ₂）₂-｛Ｏ-（ＣＨ₂）₂｝_lで表される基であり（ただし、ｌは１〜３の整数を表す）、ＳＰ２が-（ＣＨ₂）_n- で表される基である（３）に記載の積層構造体。

(Wherein R ₁₀₂ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, and SP 1 and SP 2 are each independently a single bond, a linear or branched alkylene group, or Represents a group in which two or more linear or branched alkylene groups are connected by a group selected from the group consisting of —O—, —C≡C— and —S—, and L1 and L2 are each a divalent linking group. And M represents a mesogenic group.)
The laminated structure according to (1), selected from the group consisting of compounds represented by:
(4) SP1 is a group represented by-(CH ₂ ) _m- and SP2 is a group represented by-(CH ₂ ) _n- (where m and n are each an integer of 0 to 10) The laminated structure according to (3).
(5) SP2 is _{- (CH 2) 2 - {} O- (CH 2) 2} is a group represented by _l (although, l represents an integer of 1 to 3), SP2 is - (CH ₂₎ The laminated structure according to (3), which is a group represented by _n −.

(6) A substrate for a liquid crystal cell having the laminated structure according to any one of (1) to (5) on a support.
(7) The laminated structure according to any one of (1) to (5), which is a transfer material.
(8) A method for producing a liquid crystal cell substrate comprising at least the following steps [1] and [2] in this order:
[1] A step of laminating the laminated structure according to any one of (1) to (5) on a support;
[2] A step of exposing the laminated structure on the support.
(9) A method for producing a substrate for a liquid crystal cell, comprising at least the following steps [1] to [4] in this order.
[1] A step of laminating the laminated structure according to any one of (1) to (5) on a support;
[2] Step of pattern exposure of laminated structure on substrate using photomask [3] Step of removing unexposed photosensitive resin layer and optical anisotropic layer on support (10) (8) The substrate for liquid crystal cells manufactured by the manufacturing method of (9).
(11) A liquid crystal display device having the liquid crystal cell substrate according to (6) or (10).
(12) The liquid crystal display device according to (11), wherein the liquid crystal mode is any one of STN, TN, OCB, ECB, VA, and IPS.

  By utilizing the laminated structure of the present invention, a liquid crystal display device including an optically anisotropic layer having an optical compensation capability in a liquid crystal cell can be produced without substantially increasing the number of manufacturing steps of the liquid crystal display device. . Further, the present invention provides a laminated structure of the present invention having an optically anisotropic layer comprising a liquid crystalline composition containing a compound having two or more kinds of reactive groups, the liquid crystalline compound in the liquid crystalline composition. After one polymerization reaction, another cross-linking reaction can proceed using an external stimulus such as light or heat. Therefore, the optically anisotropic layer in the liquid crystal cell substrate manufactured using the multilayer structure of the present invention has extremely high thermal stability, and is observed from an oblique direction in a liquid crystal display device having the liquid crystal cell substrate. The color change of can be suppressed.

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 at 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.

[Laminated structure]
The laminated structure of the present invention is a structure comprising at least one optically anisotropic layer and at least one photosensitive resin layer, and usually preferably has a temporary support. The laminated structure of the present invention is preferably used as a transfer material, but when used as a transfer material, it is used to transfer the optically anisotropic layer and the photosensitive resin layer onto another substrate. Material.
FIG. 1 is a schematic cross-sectional view of several examples of the laminated structure of the present invention. The laminated structure of the present invention shown in FIG. 1A has an optically anisotropic layer 12 and a photosensitive resin layer 13 on a transparent or opaque temporary support 11. The laminated structure of the present invention may have other layers. For example, as shown in FIG. 1B, between the support 11 and the optically anisotropic layer 12, there is a mating substrate at the time of transfer. It may have a layer 14 for controlling mechanical properties such as cushioning for absorbing unevenness on the side or imparting unevenness followability, and, as shown in FIG. A layer 15 functioning as an alignment layer for controlling the alignment of the liquid crystalline molecules in the crystalline layer 12 may be disposed, and may further include both layers as shown in FIG. . Moreover, you may provide the protective layer 16 which can peel in the outermost surface for the objectives, such as surface protection of the photosensitive resin layer of FIG.1 (e).

[Substrate for liquid crystal cell]
The laminated structure of the present invention is a liquid crystal including an optically anisotropic layer for compensating a viewing angle of a liquid crystal cell, which is directly attached to or transferred to a support such as a glass substrate as a part of a substrate for a liquid crystal cell. A cell substrate may be constructed. The optically anisotropic layer formed in the liquid crystal cell optically compensates for the liquid crystal cell alone or together with other optically anisotropic layers disposed outside the cell. When the laminated structure of the present invention is used as a transfer material, the photosensitive resin layer is transferred onto a transfer target (for example, a support) together with the optical anisotropic layer, and the optical anisotropic layer and the transfer target are combined. Has the function of bonding. Further, the optically anisotropic layer can be formed in a predetermined pattern using the difference in solubility between the exposed portion and the non-exposed portion of the photosensitive resin layer. Furthermore, by developing the laminated structure of the present invention as described later and using the photosensitive resin layer in the laminated structure for forming a color filter layer, the optically anisotropic layer in the laminated structure Can be an optically anisotropic layer that compensates the viewing angle for each of R, G, and B colors in the liquid crystal cell. The substrate for a liquid crystal cell to which the laminated structure of the present invention is attached or transferred may be used for either one of a pair of substrates of a liquid crystal cell, or may be used by being divided into both. . FIG. 2 shows a schematic cross-sectional view of an example of a substrate for a liquid crystal cell in which a transparent electrode layer and an alignment layer are formed on a substrate having a developed optically anisotropic layer and a photosensitive resin layer. The support 21 is not particularly limited as long as it is transparent, but a support made of a material having a small birefringence is desirable, and a support made of glass or a low birefringence polymer is used. In addition, as a material to be transferred onto which the laminated structure of the present invention is transferred, another material such as an optically anisotropic layer is provided on the above-mentioned substrate to be transferred (for example, 21 and 24 in FIG. 2B). ) May be used. A black matrix 22 and further a color filter layer 23 are formed thereon. A black matrix 22 is generally formed on a support or transfer material, and a color filter layer 23 and an optically anisotropic layer 27 made of a photosensitive resin layer patterned by mask exposure or the like are formed thereon. FIG. 2 shows an embodiment in which the color filter layers 23 of R, G, and B are formed, but as is often seen recently, a color filter layer composed of layers of R, G, B, and W (white) is formed. May be. The optically anisotropic layer 27 is divided into r, g, and b regions, and has optimum retardation characteristics for the colors of the R, G, and B filter layers 23, respectively.

  In addition to the optically anisotropic layer 27 patterned as shown in FIG. 2B, a solid optically anisotropic layer 24 may be provided. The solid optically anisotropic layer may be produced by the laminated structure of the present invention or may be produced by other methods, and the material is not particularly limited. The solid optically anisotropic layer may be on the substrate side to which the laminated structure of the present invention is transferred, or may be on the counter substrate side 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.

[Liquid Crystal Display]
FIG. 3 is a schematic cross-sectional view of an example of the liquid crystal display device of the present invention. 3 (a) and 3 (b) use the glass substrate of FIGS. 2 (a) and 2 (b) as an upper substrate, respectively, and a liquid crystal 31 with a liquid crystal 31 interposed therebetween with the glass substrate with TFT shown in 32 as an opposing substrate. This is a liquid crystal display device using the cell 37. On both sides of the liquid crystal cell 37, a polarizing plate comprising a polarizing layer 33 sandwiched between two cellulose acetate (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.

  Hereinafter, the material used for production, the production method, and the like of the laminated structure of the present invention will be described in detail. In the following, description will be made focusing on an example used as a transfer material, but the present invention is not limited to this embodiment. Other embodiments can also be produced with reference to the following description and conventionally known methods.

[Temporary support]
The laminated structure of the present invention may be provided with a temporary support, and the temporary support used may be transparent or opaque and is not particularly limited. Examples of polymers constituting the temporary support include cellulose esters (eg, cellulose acetate, cellulose propionate, cellulose butyrate), polyolefins (eg, norbornene-based polymers), poly (meth) acrylic acid esters (eg, poly Methyl methacrylate), polycarbonate, polyester and polysulfone, 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 multilayer structure of the present invention is formed from a liquid crystalline composition containing a compound having two or more types of reactive groups, and Re is not substantially 0 when the phase difference is measured. There is no particular limitation as long as it has at least one incident direction, that is, optical characteristics that are not isotropic. In the laminated structure of the present invention, the optically anisotropic layer in the liquid crystal cell substrate after transfer is preferably such that the front retardation (Re) is not substantially 0 and the in-plane slow axis is an inclined axis ( The retardation value measured by making light of wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the optically anisotropic layer as the rotation axis), and the in-plane slow axis as the inclination axis (rotation axis) ) As a layer having substantially the same retardation value measured by incidence of light having a wavelength of λ nm from a direction inclined by −40 ° with respect to the normal direction of the optically anisotropic layer. Retardation (Re) is 20 to 200 nm, and light having a wavelength of λ nm is incident from a direction inclined + 40 ° with respect to the normal direction of the optically anisotropic layer with the in-plane slow axis as the tilt axis (rotation axis). Measured retardation value It is 50~250nm.
In addition, the optically anisotropic layer in the laminated structure of the present invention is used in a liquid crystal cell, and from the viewpoint of easy control of optical properties, the liquid crystal layer containing at least one liquid crystalline compound is irradiated with ultraviolet rays. A layer formed by curing is desirable. Moreover, in order to harden | cure by ultraviolet irradiation, it is preferable that a radical polymerization initiator is included. Furthermore, when the crosslinking reaction proceeds by a method other than radical polymerization such as cationic polymerization after the formation of the optically anisotropic layer, it is preferable to include a (photo) acid generator (cationic polymerization initiator). Alternatively, a (photo) acid generator or the like can be impregnated after forming the optically anisotropic layer.

[Optically Anisotropic Layer Consisting of Liquid Crystalline Composition]
As described above, the optically anisotropic layer made of the composition containing a liquid crystal compound 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. Of course, the optically anisotropic layer alone has a sufficient viewing angle compensation ability, as well as a field of view in combination with other layers (for example, an optically anisotropic layer disposed on the opposite substrate or outside the liquid crystal cell in the liquid crystal cell). A mode that satisfies the optical characteristics required for angle compensation is also included in the scope of the present invention. The optically anisotropic layer is formed from a composition containing at least one liquid crystalline compound. In addition, the optically anisotropic layer of the laminated structure does not need to satisfy the optical characteristics sufficient for the optical compensation capability, for example, through an exposure process performed in the process of being transferred onto the liquid crystal cell substrate, The optical characteristics may be manifested or changed to finally exhibit the optical characteristics necessary for optical compensation.

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, and particularly preferably an ethylenically unsaturated group. 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). No. 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 for the transfer material can be produced by aligning uniaxial rod-like or disk-like liquid crystalline compounds 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 transparent support are parallel, and in the case of a disc-like liquid crystal, the circle of the core of the disc-like liquid crystal compound The horizontal plane of the board and the transparent support is said to be parallel, but it is not required to be strictly parallel. In the present specification, an orientation with an inclination angle of less than 10 degrees with the horizontal plane is meant. And The inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.

  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 includes a liquid crystal compound, a compound having two kinds of reactive groups described later, and a coating solution containing a liquid crystalline composition including the following polymerization initiator and other additives, and a predetermined liquid crystal composition described later. It is preferable to form by applying on the alignment layer. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Compounds having two or more reactive groups]
The optically anisotropic layer in the laminated structure of the present invention is composed of a liquid crystalline composition containing a compound having two or more reactive groups. The compound having two or more kinds of reactive groups is not particularly limited as long as it has two or more kinds, preferably two kinds of reactive groups in one molecule. Compounds are preferred. From the viewpoint of polymerization rate, one of the reactive groups is preferably a radical polymerizable group. Furthermore, the other is preferably a cationically polymerizable group that is different from the radically polymerizable group in reactivity depending on the wavelength of light to be irradiated.

As the compound having two or more reactive groups, the following (meth) acrylic compound having an oxetanyl group represented by the general formula (11) is preferable.

（式中、Ｒ₁₀₂は水素原子またはメチル基を表し、Ｒ₂は水素原子、メチル基またはエチル基を表し、ＳＰ１およびＳＰ２は、単結合、直鎖もしくは分岐アルキレン基、または２以上の直鎖もしくは分岐アルキレン基が−Ｏ−、−Ｃ≡Ｃ−および−Ｓ−からなる群から選択される基によって連結されてなる基を表し、Ｌ１およびＬ２はそれぞれ２価の連結基を表し、Ｍはメソゲン基を表す。）

(Wherein R ₁₀₂ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, and SP1 and SP2 represent a single bond, a linear or branched alkylene group, or two or more linear chains. Alternatively, a branched alkylene group represents a group formed by connecting with a group selected from the group consisting of —O—, —C≡C— and —S—, L1 and L2 each represent a divalent connecting group, and M represents Represents a mesogenic group.)

The compound represented by the general formula (11) includes a spacer unit bonded to a mesogenic moiety via a linking group, a reactive oxetanyl group at one end, and a (meth) acryl group at the other end as structural units. It is characterized by including.

As the mesogenic group, various mesogenic moieties can be used and are not particularly limited, but the following structures can be exemplified as typical examples.

As SP1 in the general formula (11), “— (CH ₂ ) _m —” (m represents an integer of 0 to 10), or “— (CH ₂ ) _m —” of ₂ or more (where m is 0) Is preferably a group connected by a group selected from the group consisting of —O—, —C≡C— and —S—, wherein “— (CH ₂ ) _m —” or two or more “— (CH _{2) m} - "(where m is not 0) group is more preferably formed by connected by the -O-," - (CH _{2) m} - "or more" - (CH _{2) 2} - "is group is more preferably formed by linked by -O-, "- (CH _{2) m} -" or _{- (CH 2) 2 - {} O- (CH 2) 2} l (l is an integer of 1 to 3 ) Is most preferred. As SP2, “— (CH ₂ ) _n —” (n represents an integer of 0 to 10), or two or more “— (CH ₂ ) _n —” (where n is not 0) is —O—, A group connected by a group selected from the group consisting of —C≡C— and —S— is preferable, and “— (CH ₂ ) _n —” or two or more “— (CH ₂ ) _n —” (provided that a group in which n is not 0) is connected by —O—, and “— (CH ₂ ) _m —”, or two or more “— (CH ₂ ) ₂ —” are connected by —O—. Is more preferable, and “— (CH ₂ ) _m —” is most preferable.
SP1 is a group represented by-(CH ₂ ) _m- and SP2 is a group represented by-(CH ₂ ) _n- , that is, a compound represented by the following formula (11) ' but more preferably, likewise SP1 is _{- (CH 2) 2 - {} O- (CH 2) 2} l - a group represented by and SP2 is - is represented by group - (CH _{2) n} It is preferable.

“— (CH ₂ ) _m —” and “— (CH ₂ ) _n —” are a single bond (where n or m is 0) or a carbon number of 1 to 10 (ie, n Or, m is a divalent linear hydrocarbon group having 1 to 10). When the target compound exhibits liquid crystallinity, the mesogen moiety and the oxetanyl group moiety and / or the mesogen moiety and the (meth) acryl group moiety may be directly bonded (single bond) without the spacer moiety (ie, SP1). May be a single bond and L1 is a single bond, and / or SP2 may be a single bond and L2 may be a single bond). Here, the oxetanyl group part means the following part.

In general, if the spacer portion between the mesogenic portion and the (meth) acrylic group portion is too short, the temperature range where liquid crystallinity is exhibited may be narrowed. If it is long, the heat resistance when a liquid crystal film is formed is adversely affected. May affect. For these reasons, it is desirable that the carbon number of the spacer portion between the mesogenic portion and the (meth) acrylic group portion is usually 1 to 8, preferably 2 to 6. Further, if the spacer portion between the mesogen portion and the oxetanyl group portion is too long, it may adversely affect the heat resistance when a liquid crystal film is formed. Therefore, the carbon number of the spacer portion between the mesogen portion and the oxetanyl group portion is usually 0 to 6, preferably 0 to 4. Here, 0 carbon atoms means a case where L2 and the oxetanyl group are directly connected by a single bond. Preferably, it has 0 carbon atoms and L2 is a single bond.

In the present invention, the linking group represented by “L1” and “L2” in the general formula (11) may be any group as long as it connects the mesogen portion and the spacer portion described above, but is preferably a single bond. , -O -, - S -, - OCO -, - COO -, - CO -, - CH 2 -, - CONH -, - NHCO -, - NHCOO -, - a OCONH-, more preferred are single A bond, —O—, —S—, —OCO—, —COO—, —CO—, —CH ₂ —, —CONH—, —NHCO—, and even more preferred are —O—, —CH _2. -. L1 is preferably —O—, and L2 is preferably a single bond. In particular, when SP1 is a single bond, L ¹ is preferably a single bond, and when SP2 is a single bond, L2 is preferably a single bond. It is particularly preferred that L1 is -O- and L2 is a single bond or L1 is -O- and L2 is -O-.

  Examples of particularly typical compounds having two types of reactive groups are shown below, but the present invention is not limited to the following examples.

A compound having two or more reactive groups may be used alone or in combination of two or more.
The content of the compound having two or more reactive groups in the liquid crystalline composition is not particularly limited as long as the liquid crystallinity of the liquid crystalline composition is not lost, but from the viewpoint of film properties, 20 mol. % Or more, preferably 50 mol% or more, more preferably 80 mol% or more. (However, mol% is the content of the liquid crystal composition with respect to all monomers.)

[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 crystalline composition. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator, and a photopolymerization reaction is more preferable. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted 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).

It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is more preferable that it is 0.5-5 mass%. Light irradiation for the polymerization of the liquid crystalline compound is preferably performed using ultraviolet rays. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under a nitrogen atmosphere or under heating conditions.

[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. 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. In order to obtain a large in-plane retardation, it is preferable to perform only polarized light irradiation or to perform polarized light irradiation 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.

When selecting the wavelength of the light to be irradiated and selectively proceeding radical polymerization and cationic polymerization, irradiate it through a low-cut filter that cuts the short wavelength side so that only radical polymerization proceeds during polarized light irradiation. Also good.
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.

[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. The post-curing of the present invention may be polarized or non-polarized, but is preferably polarized. Moreover, it is preferable to carry out post-curing twice or more, and polarized light or non-polarized light may be combined with polarized light and non-polarized light. However, when combined, it is preferable to irradiate polarized light before non-polarized light. Irradiation with ultraviolet rays may or may not be replaced with an inert gas, but is preferably performed in an inert gas atmosphere having an oxygen concentration of 0.5% or less. The irradiation energy is preferably ^{20mJ / cm 2 ~10J / cm 2} , further preferably 100 to 800 mJ / cm ^2. The illuminance is preferably 20 to 1000 mW / cm ^2, more preferably 50 to 500 mW / cm ^2, further preferably 100 to 350 mW / cm ^2. In the case of polarized light irradiation, the irradiation wavelength preferably has a peak at 300 to 450 nm, and more preferably 350 to 400 nm. In the case of non-polarized light irradiation, it preferably has a peak at 200 to 450 nm, and more preferably has a peak at 250 to 400 nm.
In the case where the radical polymerization and the cationic polymerization are selectively advanced by selecting the wavelength of the light to be irradiated, the cationic polymerization may be advanced by the post-curing. As a method, there are (1) a method of removing the low-cut filter described above and post-curing, and (2) a method of impregnating a photoacid generator after irradiation with polarized light and then post-curing by ultraviolet irradiation.

  When the optically anisotropic layer and the color filter layer are formed at the same time, the optical characteristics of the optically anisotropic layer are optimal for viewing angle compensation when R light, G light, and B light are incident. It is preferable that each of the characteristics is adjusted. That is, when the photosensitive resin layer is colored red and used for forming the R layer of the color filter, the optical characteristics of the optically anisotropic layer are optimally adjusted for viewing angle compensation when R light is incident. When colored green, the optical properties of the optically anisotropic layer are optimally adjusted for viewing angle compensation when G light is incident, and when colored blue, the optical properties of the optically anisotropic layer The characteristics are preferably adjusted optimally 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およびＲ³は各々独立して、水素原子または置換基を表し、Ｘ¹、Ｘ²およ
びＸ³は単結合または二価の連結基を表す。Ｒ¹〜Ｒ³で各々表される置換基としては、好
ましくは置換もしくは無置換の、アルキル基（中でも、無置換のアルキル基またはフッ素置換アルキル基がより好ましい）、アリール基（中でもフッ素置換アルキル基を有するアリール基が好ましい）、置換もしくは無置換のアミノ基、アルコキシ基、アルキルチオ基、ハロゲン原子である。Ｘ¹、Ｘ²およびＸ³で各々表される二価の連結基は、アルキレン基、アルケニレン基、二価の芳香族基、二価のヘテロ環残基、−ＣＯ−、―ＮＲ^a−（Ｒ^aは炭素原子数が１〜５のアルキル基または水素原子）、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−およびそれらの組み合わせからなる群より選ばれる二価の連結基であることが好ましい。二価の連結基は、アルキレン基、フェニレン基、−ＣＯ−、−ＮＲ^a−、−Ｏ−、−Ｓ−およびＳＯ₂−からなる群より選ばれる二価の連結基または該群より選ばれる基を少なくとも二つ組み合わせた二価の連結基であることがより好ましい。アルキレン基の炭素原子数は、１〜１２であることが好ましい。アルケニレン基の炭素原子数は、２〜１２であることが好ましい。二価の芳香族基の炭素原子数は、６〜１０であることが好ましい

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a substituent, and X ¹ , X ² and X ^{3 each} represent a single bond or a divalent linking group. The substituent represented by each of R ^{1 to} R ³ is preferably a substituted or unsubstituted alkyl group (more preferably an unsubstituted alkyl group or a fluorine-substituted alkyl group), an aryl group (particularly a fluorine-substituted alkyl). An aryl group having a group is preferred), a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, and a halogen atom. The divalent linking groups represented by X ¹ , X ² and X ³ are each an alkylene group, an alkenylene group, a divalent aromatic group, a divalent heterocyclic residue, —CO—, —NR ^a — ( R ^a is ^a divalent linking group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, —SO ₂ —, and combinations thereof. Preferably there is. The divalent linking group is selected from the group consisting of an alkylene group, a phenylene group, —CO—, —NR ^a —, —O—, —S—, and SO ₂ — or the group. It is more preferably a divalent linking group in which at least two groups are combined. 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 preferably the substituents represented by R ¹ , R ² and R ³ in the general formula (I). It is listed as a thing. As the horizontal alignment agent used in the present invention, the compounds described in 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 rubbing-treated layer of an organic compound (preferably a polymer), an oblique deposition layer of an inorganic compound, and a layer having a microgroove, ω-tricosanoic acid, dioctadecylmethylammonium chloride, and stearyl. Examples thereof include a cumulative film formed by Langmuir-Blodgett method (LB film) such as methyl acid, or a layer in which a dielectric is oriented by applying an electric field or a magnetic field. In the laminated structure of the present invention, 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 preferable polymers include polyimide, polystyrene, polymers of styrene derivatives, gelatin, polyvinyl alcohol and alkyl-modified polyvinyl alcohol having an alkyl group (preferably having 6 or more carbon atoms).

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

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

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

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

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

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

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the colored resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred.

(3) Photopolymerization initiator In this specification, the term (photo) polymerization initiator means (photo) polymerization initiator or (photo) polymerization initiator system.
Examples of the photopolymerization initiator include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512. Aromatic α-hydrocarbon compounds substituted with α-hydrocarbons described in US Pat. Nos. 3,046,127 and 2,951,758, triaryls described in US Pat. No. 3,549,367 Combination of imidazole dimer and p-aminoketone, benzothiazole compound and trihalomethyl-s-triazine compound described in JP-B-51-48516, trihalomethyl-triazine compound described in US Pat. No. 4,239,850 U.S. Pat. No. 4,221,976 And tri halomethyl oxadiazole compounds as described in. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

Typical examples of the photopolymerization initiator include a radical polymerization initiator that is a photoradical generator and a cationic polymerization initiator that is a photoacid generator.
(Radical polymerization initiator)
Examples of radical polymerization initiators are illustrated below.

(Cationic polymerization initiator)
Any cationic polymerization initiator may be used as long as it has an action of generating an acid by light irradiation and initiating cationic polymerization of an oxetanyl group, but an onium salt is preferred. In this case, the counter anion may be either an organic anion or an inorganic anion. Examples of the onium salt include an iodonium salt, a diazonium salt, a sulfonium salt, and the like. A sulfonium salt and an iodonium salt are preferable, and a sulfonium salt is more preferable in consideration of thermal stability. Examples of typical cationic polymerization initiators include the following examples.

In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
In the photosensitive resin layer, the photopolymerization initiators may be used singly or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
As for content of the photoinitiator with respect to the total solid of the photosensitive resin composition, 0.5-20 mass% is common, and 1-15 mass% is preferable.

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

As the colorant in the present invention, among the above-mentioned colorants, (i) R (red) colored resin composition is C.I. I. Pigment Red 254 is C.I. in (ii) G (green) colored resin composition. I. 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. The pigment red 254 is preferably 80% by mass or more, particularly preferably 90% by mass or more. C. I. The pigment green 36 is preferably 50% by mass or more, particularly preferably 60% by mass or more. C. I. Pigment Blue 15: 6 is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  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.) or 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]
In the transfer material of the present invention, between the support and the optically anisotropic layer, a thermoplastic resin layer for controlling the mechanical properties and unevenness followability of the transfer material, and when applying a plurality of coating layers, In addition, an intermediate layer that prevents mixing of components during storage after application 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-alkoxy Chill 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 described as “separation layer” in JP-A-5-72724. Time load is reduced and productivity is improved. The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

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

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

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

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

  When an optically anisotropic layer that is not patterned is formed on the transfer material, the entire surface is exposed. When an optically anisotropic layer patterned like a color filter is formed, pattern exposure is performed. In the simultaneous formation of the patterned optical anisotropy and the color filter, a predetermined mask is disposed above the optical anisotropic layer formed on the support, and then exposed from above the mask through the mask. Alternatively, exposure may be performed by focusing on a predetermined position without using a mask using a laser or an electron beam. Next, development with a developer is performed. In this exposure, the optically anisotropic layer and the color filter are cured only in the exposed portion, and the optically anisotropic layer and the color filter are in close contact with each other. By developing after mask exposure, the developer penetrates the optically anisotropic layer and dissolves the color filter in the unexposed area, creating voids and peeling off the upper optically anisotropic layer, and developing only the unexposed area. Can be patterned.

When a color filter layer is formed together with an optically anisotropic layer, 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 by development. A patterned R color is formed. An optical anisotropic layer formed in the same pattern as the color filter and its RGB pattern by performing the same process using the transfer material having the green (G) resin layer and the blue (B) resin layer, respectively. A liquid crystal cell substrate having the following can be obtained. Here, as the light source for exposure, any light source capable of irradiating light in a wavelength region capable of curing the resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

[Development of optically anisotropic layer and photosensitive resin layer with aqueous alkali solution]
Further, the developer used in the development process after exposure is not particularly limited, and a known developer such as that described in JP-A-5-72724 can be used. Is preferred. Although it does not specifically limit as aqueous alkali solution, If a typical thing is illustrated, aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, a pyridine, a triethanolamine, will be mentioned. The pH of the aqueous solution may be 7.1 to 14.0, but is preferably 7.1 to 12.0, more preferably 8.0 to 10.0 from the viewpoint of developability and waste liquid treatment. Good. The aqueous alkaline solution may contain a surfactant and an organic solvent miscible with water in order to further improve developability. As the surfactant, an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be used. Among these, anionic surfactants and nonionic surfactants are preferably used from the viewpoint of the transparency of the solution. These can also be used in combination. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone, tetrahydrofuran, acetonitrile, etc. it can. The content of these organic solvents is preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less with respect to the total solvent.

  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 preferable. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

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

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

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

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

(Preparation of coating liquid LC-R1 for optically anisotropic layer)
After preparing the following composition, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as the coating liquid LC-R1 for the optically anisotropic layer.
LC-1-1 was obtained from Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002). LC-1-2 is EP1388538A1, page
Synthesized by the method described in 21.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 12.3
Chiral agent (Paliocolor LC756, BASF Japan)
3.32
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 2.70
(However, Ph represents a 1,4-phenylene group)
4,4′-Azoxydianisole 0.52
Compound P1 13.70 above
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 0.68
Photopolymerization initiator: the above compound CA6
(DTS-103, Midori Chemical Co., Ltd.) 0.68
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) 13.05
Chiral agent (Paliocolor LC756, BASF Japan)
3.27
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 2.70
(However, Ph represents a 1,4-phenylene group)
4,4′-Azoxydianisole 0.27
Compound P2 12.70 above
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 0.68
Photopolymerization initiator: the above compound CA6
(DTS-103, Midori Chemical Co., Ltd.) 0.68
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) 4.38
Chiral agent (Paliocolor LC756, BASF Japan)
3.30
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 2.70
(However, Ph represents a 1,4-phenylene group)
4,4′-Azoxydianisole 0.03
Compound P8 21.70
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 0.68
Photopolymerization initiator: the above compound CA6
(DTS-103, Midori Chemical Co., Ltd.) 0.68
Methyl ethyl ketone 66.45
──────────────────────────────────――
(Preparation of coating liquids LC-R11, LC-G11, and LC-B11 for optically anisotropic layers)
An optically anisotropic layer coating liquid LC-R11 was prepared in the same manner as the preparation of the optically anisotropic layer coating liquid LC-R1 except that P11 was used instead of the compound P1. An optically anisotropic layer coating liquid LC-G11 was prepared in the same manner as the optically anisotropic layer coating liquid LC-G1 except that P11 was used instead of the compound P2. An optically anisotropic layer coating liquid LC-B11 was prepared in the same manner as in the preparation of the optically anisotropic layer coating liquid LC-B1 except that P11 was used instead of the compound P8.

(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) 25.92
Chiral agent (Paliocolor LC756, BASF Japan)
3.40
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 2.70
(However, Ph represents a 1,4-phenylene group)
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) 25.68
Chiral agent (Paliocolor LC756, BASF Japan)
3.34
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 2.70
(However, Ph represents a 1,4-phenylene group)
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) 26.02
Chiral agent (Paliocolor LC756, BASF Japan)
3.36
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 2.70
(However, Ph represents a 1,4-phenylene group)
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 2 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 (%)
────────────────────────────────────────
Random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio (weight average molecular weight 30,000) 27.0
Propylene glycol monomethyl ether acetate 73.0
──────────────────────────────────────――

[Binder 3 composition]
──────────────────────────────────────――
Binder 3 composition (%)
──────────────────────────────────────――
Random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate = 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 solution PP-K1 for the photosensitive resin layer was first weighed in the amounts of K pigment dispersion and propylene glycol monomethyl ether acetate listed in Table 1, 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 1 Bromophenyl] -s-triazine and Megafac F-176PF were 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. .

(Preparation of coating solution PP-R1 for photosensitive resin layer)
The coating liquid PP-R1 for the photosensitive resin layer was first weighed in the amounts of R pigment dispersion-1, R pigment dispersion-2 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, and the temperature was 24 ° C. (± 2 ° C. ) And stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxax described in Table 1 Diazole, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine were weighed out and the temperature was 24 ° C. (± 2 In this order and stirred at 150 rpm for 10 minutes, then weighed out the amount of ED152 listed in Table 2 and mixed at a temperature of 24 ° C. (± 2 ° C.) to 150 rp The mixture was stirred for 20 minutes, and the amount of Megafac F-176PF shown in Table 2 was weighed out, 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 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-styrylstyryl) -1,3,4-oxadiazole in the amounts listed in Table 2, 4-Bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine are weighed out in this order at a temperature of 24 ° C. (± 2 ° C.). Add and stir at 150 rpm for 30 minutes, and then weigh out the amount of Megafac F-176PF listed in Table 2 to a temperature of 2 It was obtained by adding at 4 ° C. (± 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-styrylstyryl) -1,3,4-oxadiazole, phenothiazine, as listed in Table 2, They were added in this order at a temperature of 25 ° C. (± 2 ° C.), stirred at a temperature of 40 ° C. (± 2 ° C.) at 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)
On a polyethylene terephthalate roll film temporary support having a thickness of 75 μm, the coating liquid CU-1 for thermoplastic resin layer was applied and dried using a slit nozzle. Next, the intermediate layer / alignment layer coating solution AL-1 was applied and dried. 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 a black matrix, in which the temporary support, the thermoplastic resin layer, the intermediate layer / alignment layer, 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 optically anisotropic layer transfer material for RGB: including compounds having two types of reactive groups)
On a polyethylene terephthalate roll film temporary support having a thickness of 75 μm, the coating liquid CU-1 for thermoplastic resin layer was applied and dried using a slit nozzle. Next, the alignment layer coating liquid AL-1 was applied and dried. The film thickness of the thermoplastic resin layer was 14.6 μm, and the alignment layer was 1.6 μm. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-R1 for optically anisotropic layer is applied thereon with a # 6 wire bar coater, and the film surface temperature is 95 ° C. for 2 minutes by heating and aging. And a layer having a uniform liquid crystal phase was formed. Further, immediately after aging, this layer was irradiated with polarized UV using POLUV-1 so that the transmission axis of the polarizing plate was in the TD direction of the transparent support in a nitrogen atmosphere with an oxygen concentration of 0.3% or less. (Illuminance 200 mW / cm ²
The optical anisotropic layer was fixed by applying an irradiation amount of 200 mJ / cm ² ) to form an optically anisotropic layer having a thickness of 2.8 μm. Finally, the photosensitive resin composition PP-R1 was applied and dried to form a photosensitive resin layer having a thickness of 1.6 μm, thereby preparing 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 film thicknesses of the optically anisotropic layers G-1 and B-1 were 2.75 μm and 2.3 μm, respectively.
Further, an R transfer material R-11 was produced by the same method as the production of the R transfer material R-1, except that LC-R11 was used instead of LC-R1. A transfer material G-11 for G was prepared in the same manner as the preparation of the transfer material G-1 for G except that LC-G11 was used instead of LC-G1. A transfer material B-11 for B was prepared in the same manner as the transfer material B-1 for B except that LC-B11 was used instead of LC-B1.
The film thicknesses of the optically anisotropic layers of R-11, G-11, and B-11 were 1.5 μm, 2.7 μm, and 2.3 μm, respectively.

(Preparation of RGB optically anisotropic layer transfer material: not including compounds having two types of reactive 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.

(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 of the present invention is calibrated with the transmittance data of the color filter measured in advance, so that the phase difference of the optically anisotropic layer having a phase difference among the transfer materials solid-transferred to the glass is obtained. Only asked for. Table 2 shows the phase difference measurement results.

(Example 1: Production of color filter)
A color filter was produced by the following method.
-Formation of black (K) image-
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) γ-aminopropyltrimethoxysilane 0.3%
Aqueous solution, trade name: KBM-603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
After peeling off the protective film of the photosensitive resin 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 off the protective film, the exposure mask surface with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. The distance between the photosensitive resin layer 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 (containing 2.5% triethanolamine, containing a nonionic surfactant, containing a polypropylene 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 / 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.) was used for shower development at a cone type nozzle pressure of 0.15 MPa for 1 minute to develop the photosensitive resin layer to obtain a patterned pixel.
Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) at a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a shower and a rotating brush having nylon bristles to obtain a black (K) image, which was further irradiated with 500 mJ / cm ² of light from the resin layer side to the substrate with an ultrahigh pressure mercury lamp. 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-
On the substrate on which a black (K) image is formed using the photosensitive resin transfer material R-1, red (R) pixels and 28 × 28 μm in the same process as the photosensitive resin transfer material K-1. A square red (R) pattern was formed. However, the exposure amount was 40 mJ / cm ² . The substrate on which the R pixel was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-Green (G) image formation-
On the substrate on which the red (R) pixel is formed using the photosensitive resin transfer material G-1, the green (G) pixel and the red are formed in the same process as the photosensitive resin transfer material K-1. A green (G) pattern was formed on the (R) pattern so as to cover the entire red (R) pattern. However, the exposure amount was 40 mJ / cm ² . The substrate on which the R and G images were 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 blue (B) image-
Blue (B) pixels are formed on the substrate on which the red (R) pixels and green (G) pixels are formed using the photosensitive resin transfer material B-1 in the same process as the photosensitive resin transfer material K1. Got. However, the exposure amount was 30 mJ / cm ² . The substrate on which the R, G, and B pixels are formed is again cleaned with a brush as described above. 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 the color filter of Example 1.
(Example 11: Production of color filter)
A color filter of Example 11 was produced in the same manner as in Example 1 except that R-11, G-11, and B-11 were used instead of R-1, G-1, and B-1, respectively.
(Reference Example 1: Production of color filter)
R-1, G-1, and B-1 were changed to R-2, G-2, and B-2, and the same operation as in Example 1 was performed.

(Formation of transparent electrode)
A transparent electrode film was formed on the color filter produced in Example 1 by sputtering of ITO.

(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 (Fuji Film Electronics Materials Co., Ltd.)
53.3
Methyl ethyl ketone 46.66
Mega Fuck F-176PF 0.04
──────────────────────────────────――
Further, a 12 μm-thick polypropylene film is attached to the surface of the photosensitive resin layer as a cover film, and a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer, and a cover film are laminated in this order on the temporary support. A transfer material was prepared.

(Forming protrusions)
The cover film is peeled off from the projection transfer material produced above, and the surface of the photosensitive resin layer and the surface of the color filter side substrate obtained in Example 1 on which the ITO film is provided are overlaid, and a laminator (A Hitachi Industries, Ltd. (Lamic II type)) was used for bonding 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, a protrusion made of a photosensitive resin layer patterned into a desired shape was formed on the color filter side substrate. Next, the color filter side substrate on which the protrusions are formed is baked at 240 ° C. for 50 minutes to form a liquid crystal alignment control protrusion having a height of 1.5 μm and a vertical cross-sectional shape on the color filter side substrate. Could be formed.

(Formation of alignment layer)
Further, a polyimide alignment film was provided thereon. A sealant of epoxy resin containing spacer particles is printed at a position corresponding to the outer frame of the black matrix provided around the color filter pixel group, and the color filter substrate is placed on the counter substrate (the TFT layer on the glass substrate). It was pasted together at 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.

(VA-LCD of Example 2)
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 2 was produced.
(VA-LCD of Example 12)
The VA-LCD of Example 12 was prepared in the same manner as the VA-LCD of Example 2 except that the color filter obtained in Example 11 was used instead of the color filter obtained in Example 1. Was made.

(Reference Example 2: Production of VA-LCD)
The VA-LCD of Reference Example 2 was prepared in the same procedure as that of the VA-LCD of Example 2 except that the color filter obtained in Reference Example 1 was used instead of the color filter prepared in Example 1. Produced.

(Evaluation of VA-LCD)
The viewing angle characteristics of the manufactured liquid crystal display device were measured with a viewing angle measuring device (EZ Contrast 160D, manufactured by ELDIM). For Example 2, Example 12, and Reference Example 2, when the viewing angle is changed by 0 to 80 degrees rightward, 45 degrees above right, and upwards from the front of the LCD during black display (no voltage applied) The color change on the xy chromaticity diagram is shown in FIG.

It is a schematic sectional drawing of an example of the laminated structure of this invention. It is a schematic sectional drawing of an example of the board | substrate for liquid crystal cells produced using the laminated structure of this invention as a transfer material. It is a schematic sectional drawing of an example of the liquid crystal display device of this invention. It is a figure which shows the color viewing angle characteristic of VA-LCD produced in Example 2 and Reference Example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Temporary support body 12 Optical anisotropic layer 13 Photosensitive resin layer 14 Mechanical property control layer 15 Orientation control layer 16 Protection layer 21 Support body 22 Black matrix 23 Color filter layer 24 Solid optical anisotropic layer 25 Transparent electrode layer 26 Orientation 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 37 Liquid crystal cell

Claims (12)

A laminated structure comprising at least one optically anisotropic layer made of a liquid crystalline composition containing a compound having two or more kinds of reactive groups, and at least one photosensitive resin layer. The two or more reactive groups are two or more groups selected from the group consisting of acryloyl group, methacryloyl group, oxetanyl group, epoxy group, alkoxysilyl group, allyl group, acrylamide group, and vinyloxycarbonyl group. The laminated structure according to claim 1. The compound is represented by the following general formula (11):

(Wherein R ₁₀₂ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, and SP 1 and SP 2 are each independently a single bond, a linear or branched alkylene group, or Represents a group in which two or more linear or branched alkylene groups are connected by a group selected from the group consisting of —O—, —C≡C— and —S—, and L1 and L2 are each a divalent linking group. And M represents a mesogenic group.)
The laminated structure according to claim 1, which is selected from the group consisting of compounds represented by: SP1 is a group represented by-(CH ₂ ) _m- and SP2 is a group represented by-(CH ₂ ) _n- (where m and n each represents an integer of 0 to 10) The laminated structure according to claim 3. SP1 is _{- (CH 2) 2 - {} O- (CH 2) 2} is a group represented by _l (although, l represents an integer of 1 to 3), SP2 is - (CH _{2) n} - ( However, n is a group represented by the integer of 0-10) The laminated structure of Claim 3. The liquid crystal cell substrate which has the laminated structure as described in any one of Claims 1-5 on a support body. It is a transfer material, The laminated structure as described in any one of Claims 1-5. A method for producing a liquid crystal cell substrate comprising at least the following steps [1] and [2] in this order:
[1] Laminating the laminated structure according to any one of claims 1 to 5 on a support;
[2] A step of exposing the laminated structure on the support. A method for producing a substrate for a liquid crystal cell, comprising at least the following steps [1] to [4] in this order.
[1] Laminating the laminated structure according to any one of claims 1 to 5 on a support;
[2] Step of pattern exposure of laminated structure on substrate using photomask [3] Step of removing unexposed photosensitive resin layer and optical anisotropic layer on support A liquid crystal cell substrate manufactured by the manufacturing method according to claim 8. A liquid crystal display device comprising the liquid crystal cell substrate according to claim 6. The liquid crystal display device according to claim 11, wherein the liquid crystal mode is any one of STN, TN, OCB, ECB, VA, and IPS.

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