JP2010085690A - Tn mode liquid crystal cell and tn mode liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a TN mode liquid crystal cell which is high in contrast in an oblique direction and low in a color shift in the oblique direction when a black is displayed; and to provide a TN mode liquid crystal display. <P>SOLUTION: The TN mode liquid crystal cell includes: a pair of substrates; a liquid crystal layer arranged within the pair of substrates; a color filter layer which is arranged on the inner face of at least one of the substrates and includes a plurality of colored layers having mutually different color phases; and phase-different layers which are arranged in areas in the inner face of the substrate having the color filter layer or in the inner face of another substrate, the areas corresponding to the colored layers of the color filter layer. In this case, the phase-different layers contain a disk-shaped liquid crystallin compound which is fixed in an alignment state, and their optical characteristics are different in the areas from each other in accordance with the color phases of the corresponding colored layers. The TN mode liquid crystal device includes the liquid crystal cell concerned. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a so-called in-cell type TN mode liquid crystal cell and a TN mode liquid crystal display device having a retardation layer having optical compensation capability in a cell.

Conventionally, TN mode liquid crystal display devices have been put into practical use and widely used as liquid crystal display devices for personal computers (PC). Usually, in the TN mode liquid crystal display device, a retardation layer having an action of compensating for the birefringence of the liquid crystal cell is disposed between the liquid crystal cell and each of the pair of substrates, thereby achieving a wide viewing angle. .
As for liquid crystal display devices, a so-called in-cell method in which retardation layers having various characteristics are arranged in a liquid crystal cell for the purpose of improving display performance and the like is a VA mode liquid crystal display device (for example, Patent Document 1 and 2) and a transflective liquid crystal display device (for example, Patent Document 3).
JP 2006-78647 A JP 2007-193090 A JP 2007-101645 A

  In recent years, liquid crystal display devices have been used not only as displays for PCs but also for TVs. A large TV is required to have a wider viewing angle characteristic than a PC display because a plurality of observers observe from various directions. For the TN mode liquid crystal display device, in order to satisfy the characteristics as a TV display, it is necessary to further improve the display performance. In particular, the contrast in the oblique direction is improved, and the color shift in the oblique direction during black display. Relief is needed.

  It is an object of the present invention to provide a TN mode liquid crystal cell and a TN mode liquid crystal display device having high contrast in an oblique direction and small color shift in an oblique direction during black display.

Means for solving the above problems are as follows.
[1] a pair of substrates;
A liquid crystal layer disposed between the pair of substrates;
A color filter layer comprising a plurality of colored layers having different hues disposed on at least one inner surface of the pair of substrates;
A retardation layer disposed in a region corresponding to the colored layer of the color filter layer, which is an inner surface of the substrate having the color filter layer or the other substrate,
The TN mode liquid crystal cell, wherein the retardation layer contains a discotic liquid crystal compound fixed in an aligned state, and the optical characteristics thereof are different between regions depending on the hue of the corresponding colored layer .
[2] The TN mode liquid crystal cell according to [1], wherein among the plurality of colored layers of the color filter layer, at least two colored layers having different hues have different thicknesses.
[3] The color filter layer includes a red (R) layer, a green (G) layer, and a blue (B) layer, and at least the thickness of the B layer is larger than the thickness of the R layer and the G layer. The TN mode liquid crystal cell according to [2], wherein a thickness of a region of the liquid crystal layer corresponding to the B layer is smaller than a region of the liquid crystal layer corresponding to the R layer and the G layer.
[4] The thickness of the retardation layer differs between a plurality of regions of the retardation layer according to the hue of the corresponding colored layer, and accordingly, the in-plane retardation Re of the retardation layer is compatible. The TN mode liquid crystal cell according to any one of [1] to [3], wherein the plurality of regions differ from each other according to the hue of the colored layer to be formed.
[5] The color filter layer includes a red (R) layer, a green (G) layer, and a blue (B) layer, and the thickness of the region corresponding to the B layer of the retardation layer is the R layer and the G layer. The TN mode liquid crystal cell according to [4], wherein the TN mode liquid crystal cell is smaller than the thickness of the region corresponding to.
[6] The TN mode liquid crystal cell according to any one of [1] to [5], wherein the retardation layer is provided on both inner surfaces of the pair of substrates.
[7] A TN mode liquid crystal display device comprising the liquid crystal cell according to any one of [1] to [6].

  According to the present invention, it is possible to provide a TN mode liquid crystal cell and a TN mode liquid crystal display device having high contrast in an oblique direction and small color shift in an oblique direction during black display.

Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. .
The present invention relates to a so-called in-cell TN mode liquid crystal cell having a retardation layer for optical compensation in the liquid crystal cell. The liquid crystal cell of the present invention has a retardation layer containing a discotic liquid crystal compound fixed in an aligned state on the inner surface of at least one substrate of the liquid crystal cell. The optical characteristics of the retardation layer differ from region to region depending on the hue of the colored layer of the color filter layer. Here, the optical characteristics of the retardation layer refer to in-plane retardation Re and thickness direction retardation Rth, and a measuring method will be described later.
In the present invention, a retardation layer produced using a discotic liquid crystal compound is disposed in a liquid crystal cell, and the optical characteristics are varied between regions according to the hue of each colored layer of the color filter layer. Therefore, the optical compensation of the TN mode liquid crystal cell can be performed more accurately. As a result, the contrast in the oblique direction can be improved, and the color shift in the oblique direction during black display can be reduced.

  In an aspect having a color filter layer including a red (R) layer, a green (G) layer, and a blue (B) layer as a color filter layer, a region corresponding to at least the B layer of the retardation layer disposed in the cell In other words, the in-plane retardation Re and / or the thickness direction retardation Rth of the retardation layer region corresponding to the B layer of the retardation layer is preferably set to a value corresponding to the R layer and the G layer. It is preferable to make it smaller than Re and / or Rth in the region of the phase difference layer. More preferably, the retardation layer is formed such that the thickness increases in the order of the retardation layer region corresponding to the B layer, the retardation layer region corresponding to the G layer, and the retardation layer region corresponding to the R layer. Is preferably formed. The retardation layer is a uniform layer, or is formed only in regions corresponding to the R layer, the G layer, and the B layer, and is an aggregate of a plurality of layers separated into minute regions. It may be.

  As described above, the present invention relates to an in-cell type TN mode liquid crystal cell. Furthermore, a higher effect can be expected for an aspect combined with a multi-gap type. Here, the multi-gap liquid crystal cell refers to a liquid crystal cell in which the cell gap, that is, the thickness of the liquid crystal layer is different between regions depending on the hue of the colored layer of the color filter layer. A multi-gap liquid crystal layer can be obtained by varying the thickness of each colored layer of the color filter according to the hue. For example, in an aspect having a color filter layer including a red (R) layer, a green (G) layer, and a blue (B) layer as the color filter layer, at least the thickness of the B layer is greater than the thickness of the R layer and the G layer. Therefore, it is preferable that the thickness of the region of the liquid crystal layer corresponding to the B layer is smaller than the region of the liquid crystal layer corresponding to the R layer and the G layer. More preferably, the thickness of the liquid crystal layer is increased in the order of the liquid crystal layer region corresponding to the B layer, the liquid crystal layer region corresponding to the G layer, and the liquid crystal layer region corresponding to the R layer.

  Conventionally, two retardation films are used for optical compensation of a TN mode liquid crystal cell, and one is generally disposed between a pair of substrates and a liquid crystal cell. The liquid crystal cell of the present invention may have only one phase difference layer in the cell, or may have two phase difference layers in the cell. In the latter mode, the two retardation layers are arranged one layer on each inner surface of the pair of cell substrates. In the latter mode, it is preferable that both of the two retardation layers have different optical characteristics between a plurality of regions in accordance with the hue of the colored layer of the color filter. Of course, the other optical characteristics may be uniform.

FIG. 1 shows a schematic cross-sectional view of an example of a liquid crystal cell substrate that can be used in the liquid crystal cell of the present invention. The relative relationship between the size and thickness of each layer in the figure does not necessarily match the actual relative relationship between the size and thickness of each layer. The same applies to the other drawings.
The liquid crystal cell substrate shown in FIG. 1 has an R (red) layer 3R and a G (green) layer 3G separated on the surface of a substrate 1 made of glass or the like by a light shielding layer 2 serving as a black matrix and a light shielding layer 2, respectively. , And a B (blue) layer 3B (hereinafter, each colored layer may be referred to as a “micro color filter”), an in-cell retardation layer 4, and a transparent electrode layer 5 made of ITO or the like.

  In the substrate shown in FIG. 1, the formed colored layers, the R layer 3R, the G layer 3G, and the B layer 3B have different film thicknesses. Therefore, the in-cell retardation layer 4 formed on each colored layer is different. The film thicknesses of the regions 4r, 4g, and 4r corresponding to 3R, 3G, and 3B are also different from each other. As a result, the thickness of the in-cell retardation layer can be changed according to the hue of the colored layer, and the retardation value of the in-cell retardation layer can be optimized for each color. The thicknesses dr, db, and db of the in-cell retardation layer 4 disposed at positions corresponding to the R layer, the G layer, and the B layer preferably satisfy db <dr and db <dg, and db <dg It is more preferable to satisfy <dr.

  The liquid crystal cell substrate shown in FIG. 1 is formed, for example, by forming a color filter 3 composed of a plurality of colored layers having different thicknesses on the surface of a substrate 1 having a uniform surface, and then applying or transferring it. The in-cell retardation layer 4 can be produced by forming the surface to be uniform. In a configuration in which the substrate, color filter, and in-cell retardation layer are formed in this order, the thickness of the color filter is changed for each color (red, green, and blue) to optimize the optical characteristics of the in-cell retardation layer. The method is preferred.

  Thickness d (CFR), d (CFG), d (CFB) of each color (red, green, blue) colored layer, R (red) layer 3R, G (green) layer 3G, and B (blue) layer 3B ) Preferably satisfies d (CFR) <d (CFB) and d (CFG) <d (CFB), and more preferably satisfies d (CFR) <d (CFG) <d (CFB).

  The substrate 1 can have a single-layer structure or a multi-layer structure depending on a desired function or the like. When the substrate 1 has a single layer structure, the substrate 1 can be formed of an inorganic material such as glass or an organic material such as resin. When the substrate 1 has a multi-layer structure, the structure can be appropriately selected according to the desired function of the liquid crystal cell substrate, and even in this case, the layer serving as the base of the in-cell optical compensation layer 4 is: It is preferably formed of an inorganic material such as glass or an organic material such as resin. The substrate 1 is preferably optically isotropic, but a light shielding region or the like can be locally provided as necessary. The light transmittance of the substrate 1 can be appropriately selected according to the desired function of the liquid crystal cell substrate.

  The in-cell retardation layer 4 formed on the substrate 1 is a layer made of a liquid crystalline composition containing a discotic liquid crystal compound. The layer is preferably formed by hybridly aligning disk-like liquid crystal molecules and fixing them in that state.

  The color filter 3 is a primary color system in which a red micro color filter 3R, a green micro color filter 3G, and a blue micro color filter 3B are arranged in a predetermined pattern. The arrangement of the micro color filters 3R, 3G, and 3B for each color is not particularly limited, and may be any of various arrangements called a stripe type, a mosaic type, and a triangle type. It is also possible to use a complementary color filter instead of the primary color filter.

  For example, the color filter 3 is formed by patterning a coating film of a color resin, which is a material, for each micro color filter 3R, 3G, 3B for each color into a predetermined shape by, for example, a photolithography method, or for each color micro color filter Each of the filters 3R, 3G, and 3B can be formed by applying a color filter ink as a material thereof in a predetermined shape.

  The light shielding layer 2 is for preventing light leakage (leakage light) from between pixels in the display liquid crystal panel and light deterioration of the active element in the active matrix drive type display liquid crystal panel. Individual pixels are defined on the panel in plan view. The colored layers 3R, 3G, and 3B for the respective colors are arranged so as to cover predetermined pixels defined by the light shielding layer 2 in plan view.

  The light shielding layer 2 can be formed by patterning a metal thin film having a light shielding property or a light absorbing property such as a metal chromium thin film or a tungsten thin film into a predetermined shape. It is also possible to form the light shielding layer 2 by printing an organic material such as a black resin in a predetermined shape. In addition, it is also possible to use a monochromatic color filter as the color filter 3, and in this case, the light shielding layer 2 can be omitted.

  As shown in FIG. 1, when the unevenness formed by the thickness of each colored layer of the color filter layer 3 is flattened by the retardation layer 4, the orientation of the liquid crystal molecules in the liquid crystal layer is not disturbed. Therefore, it is preferable.

  Although FIG. 1 shows an example in which the in-cell retardation layer 4 is disposed on the color filter 3, the in-cell retardation layer 4 is disposed between the inner surface of the substrate 1 and the color filter 3. However, the same effect can be obtained.

Although FIG. 1 shows an example of a substrate in which an in-cell retardation layer is arranged on the same substrate as that on which a color filter is arranged, the cell substrate that can be used in the present invention is not limited to the above embodiment. Absent. For example, a substrate having an in-cell retardation layer on the substrate side on which the color filter is not disposed as shown in FIG. 2 may be used. In addition, the same code | symbol is attached | subjected to the functional layer same as FIG.
The liquid crystal cell substrate of FIG. 2 is a surface of a substrate 1 ′ made of glass or the like, and in a region corresponding to the B layer of the color filter disposed on the other substrate surface, the planarizing layer 6b and A planarizing layer 6g is provided in a region corresponding to the G layer. When the retardation layer 4 ′ is formed on the surface of the substrate 1 ′ by coating or transfer, the thickness db ′ of the retardation layer region 4 b ′ corresponding to the B layer and the retardation layer region 4 g ′ corresponding to the G layer. The thickness dg 'of each of the in-cell retardation layers 4' disposed at positions corresponding to the R layer, the G layer, and the B layer is reduced by the presence of the flattening layers 6b and 6g. dr ′, dg ′, and db ′ satisfy db ′ <dg ′ <dr ′. However, as described above, if db ′ <dg ′ and db ′ <dr ′ are satisfied (that is, only the flattening layer 6b is present in the region corresponding to the B layer of the color filter disposed on the other substrate surface). Even if the planarization layer 6g is present), the effect of the present invention can be obtained.

  The liquid crystal cell substrate shown in FIG. 1 is preferably combined with the liquid crystal cell substrate shown in FIG. 2 because the effects of the present invention are further enhanced. For example, as shown in FIG. 3, the cell substrate shown in FIG. 1 is used as the display surface side liquid crystal cell substrate S1, and the cell substrate shown in FIG. 3 is used as the backlight side liquid crystal cell substrate S2. The TN mode liquid crystal cell in which the liquid crystal layer 8 made of a material is disposed is a preferred embodiment of the TN mode liquid crystal cell of the present invention. As shown in FIG. 3, it is preferable to dispose the alignment layer 7 on the surface in contact with the liquid crystal layer 8 and to twist the liquid crystal layer. As the alignment layer 7, various alignment films conventionally used for TN mode liquid crystal cells can be used.

  Further, the liquid crystal cell substrate shown in FIG. 1 is planarized in a region corresponding to the B layer of the color filter 3 and a planarized layer (however, corresponding to the B layer in the region corresponding to the G layer of the color filter 3). When a liquid crystal cell is manufactured in combination with a substrate having a thickness smaller than that of the planarization layer in the region, the presence of the planarization layer results in a multi-gap liquid crystal cell. The optical compensation optimization effect by the gap is also obtained, which is preferable.

  Also, by combining the liquid crystal cell substrate shown in FIG. 2 with a substrate having a color filter layer having a thickness increased in the order of the R layer, the G layer, and the B layer, the difference in the thickness of each colored layer. A multi-gap liquid crystal cell is preferable because not only the effect of the in-cell retardation layer but also the effect of optimizing the optical compensation by the multi-gap can be obtained.

  In FIGS. 1 and 2, the transparent electrode layer has a uniform thickness. However, the thickness of the functional layer other than the color filter layer, such as the transparent electrode layer, has a difference between regions, so that the in-cell phase difference is obtained. The thickness of the retardation layer of the layer can be different from region to region, and the thickness of the liquid crystal layer can also be different from region to region, that is, a multi-gap structure.

There is no restriction | limiting in particular about the thickness of the phase difference layer arrange | positioned in a cell. The thickness may be the same as that of a retardation layer made of a liquid crystal composition disposed outside a conventional cell. The thickness of the retardation layer disposed in the cell is preferably about 0.1 to 20 μm, more preferably about 0.1 to 10 μm. In order to obtain the effect of the present invention by changing the thickness of the region of the retardation layer corresponding to at least one color (preferably the B layer), it corresponds to the thickness of the corresponding region of the layer and other colored layers. It is preferable to vary the thickness of the region to be changed by 1 to 550 nm, and more preferably 50 to 500 nm.
In addition, as the in-plane retardation Re, the Re of the retardation layer in the region corresponding to the B layer is 0.1 to 16% compared with the Re of the retardation layer in the region corresponding to the G layer and the R layer. It is preferably about 2 nm, more preferably about 1.6 to 15.6 nm.

  1 and 2 show an embodiment in which the optical compensation action is optimized by changing the thickness of the retardation layer disposed in the cell between the regions. An aspect in which the optical characteristics are different between the regions of the retardation layer depending on the hue of the colored layer of the filter is also included in the present invention. In the present invention, the in-cell retardation layer contains a discotic liquid crystal compound fixed in an alignment state. However, the fixed alignment state may be varied between regions of the retardation layer. More specifically, the discotic liquid crystal compound can be fixed in alignment states with different tilt angles to form each region, and the optical characteristics between the regions of the retardation layer can be made different.

The in-cell retardation layer can be formed from a composition containing a discotic liquid crystal compound (sometimes referred to as a “discotic liquid crystal compound”). Regarding discotic liquid crystal compounds, various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystals). Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985), J. Zhang et al., J. Am. Chem.Soc., Vol.116, page 2655 (1994)). The polymerization of the discotic liquid crystal compound is described in JP-A-8-27284.
In order to fix the discotic liquid crystal compound by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystal compound. However, when the polymerizable group is directly connected to the disc-shaped core, it becomes difficult to maintain the orientation state in the polymerization reaction. Therefore, a linking group is introduced between the discotic core and the polymerizable group. Therefore, the discotic liquid crystal compound having a polymerizable group is preferably a compound represented by the following formula (A).

(A) D (-LP) _n
Where D is a discotic core; L is a divalent linking group; P is a polymerizable group; and n is an integer from 4 to 12.
An example of the disk-shaped core (D) is shown below. In each of the following examples, LP (or PL) means a combination of a divalent linking group (L) and a polymerizable group (P).

  Examples of the discotic liquid crystal compound used for producing the retardation layer include paragraph number [0052] in JP-A-2006-76992, and paragraph number [0040] to JP-A-2007-2220. [0063] The compound described in [0063] is preferable, for example, a compound represented by the following general formula (D16) is preferable. These discotic liquid crystal compounds are preferable because they exhibit high birefringence. Among the compounds represented by the following general formula (D16), a compound showing a discotic nematic phase is particularly preferable.

  Further, preferable examples of the discotic liquid crystal compound include compounds described in JP-A-2005-301206.

  A liquid crystal compound as described in JP-A-2007-102205 has a birefringence wavelength dispersion that is closer to the birefringence wavelength dispersion of the liquid crystal compound in the liquid crystal cell, and therefore can be preferably used. Particularly preferred skeletons are shown below.

In formula (A), the divalent linking group (L) is selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, —CO—, —NH—, —O—, —S—, and combinations thereof. A divalent linking group is preferred. The divalent linking group (L) is a divalent group in which at least two divalent groups selected from the group consisting of an alkylene group, an arylene group, -CO-, -NH-, -O-, and -S- are combined. More preferably, it is a connecting group. The divalent linking group (L) is most preferably a divalent linking group in which at least two divalent groups selected from the group consisting of an alkylene group, an arylene group, -CO- and -O- 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 in the arylene group is preferably 6-10.
Examples of the divalent linking group (L) are shown below. The left side is bonded to the discotic core (D), and the right side is bonded to the polymerizable group (P). AL represents an alkylene group or an alkenylene group, and AR represents an arylene group. The alkylene group, alkenylene group and arylene group may have a substituent (eg, an alkyl group).

L1: -AL-CO-O-AL-
L2: -AL-CO-O-AL-O-
L3: -AL-CO-O-AL-O-AL-
L4: -AL-CO-O-AL-O-CO-
L5: -CO-AR-O-AL-
L6: -CO-AR-O-AL-O-
L7: -CO-AR-O-AL-O-CO-
L8: -CO-NH-AL-
L9: -NH-AL-O-
L10: -NH-AL-O-CO-
L11: -O-AL-
L12: -O-AL-O-
L13: -O-AL-O-CO-
L14: -O-AL-O-CO-NH-AL-
L15: -O-AL-S-AL-
L16: -O-CO-AR-O-AL-CO-
L17: -O-CO-AR-O-AL-O-CO-
L18: -O-CO-AR-O-AL-O-AL-O-CO-
L19: -O-CO-AR-O-AL-O-AL-O-AL-O-CO-
L20: -S-AL-
L21: -S-AL-O-
L22: -S-AL-O-CO-
L23: -S-AL-S-AL-
L24: -S-AR-AL-

  The polymerizable group (P) in the formula (A) is determined according to the type of polymerization reaction. Examples of the polymerizable group (P) are shown below.

The polymerizable group (P) is preferably an unsaturated polymerizable group (P1, P2, P3, P7, P8, P15, P16, P17) or an epoxy group (P6, P18). More preferably, it is most preferably an ethylenically unsaturated polymerizable group (P1, P7, P8, P15, P16, P17).
In formula (A), n is an integer of 4-12. A specific number is determined according to the type of the disk-shaped core (D). In addition, although the combination of several L and P may differ, it is preferable that it is the same.

  In the liquid crystal composition, the liquid crystal compound is preferably 50% by mass to 99.9% by mass, and 70% by mass to 99.9% by mass with respect to the total amount of the composition (solid content when a solvent is included). More preferably, 80 mass%-99.5 mass% is still more preferable.

Along with the above liquid crystal compound, the liquid crystalline composition is used in combination with a plasticizer, a surfactant, a polymerizable monomer, etc., to improve the uniformity of the coating film, the strength of the film, the orientation of the liquid crystal compound, etc. be able to. These materials are preferably compatible with the liquid crystal compound and do not inhibit the alignment.
Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in paragraph numbers [0018] to [0020] in JP-A No. 2002-296423. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.

  The polymer used with the liquid crystal compound is preferably capable of thickening the coating solution. A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph [0178] of JP-A No. 2000-155216. The amount of the polymer added is preferably 0.1 to 10% by mass and more preferably 0.1 to 8% by mass with respect to the liquid crystal molecules so as not to inhibit the alignment of the liquid crystal compound.

  Examples of the surfactant include conventionally known compounds, but fluorine compounds are preferable. Specifically, for example, compounds described in paragraph Nos. [0028] to [0056] in JP-A No. 2001-330725, and paragraphs [0069] to [0126] described in JP-A No. 2005-062673 are described. Compounds. Particularly preferred examples include the fluoroaliphatic group-containing polymers described in paragraphs [0054] to [0109] of JP-A-2005-292351.

The retardation layer is formed by applying a liquid crystalline composition containing the above components onto the surface of the alignment film (preferably a rubbing surface), aligning it at a liquid crystal phase-solid phase transition temperature or lower, and then by UV irradiation. It can be formed by advancing the polymerization reaction and fixing the liquid crystal compound in its alignment state. The liquid crystal composition can be applied by a known method (eg, bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method). The liquid crystal phase-solid phase transition temperature is preferably 70 ° C to 300 ° C, particularly preferably 70 ° C to 170 ° C. As the polymerization reaction of the liquid crystal compound, a photopolymerization reaction is performed. Irradiation for polymerizing the liquid crystal compound is preferably performed using ultraviolet light, radiation energy is preferably 20~5000mJ / cm ^2, further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, the light irradiation may be carried out under heating conditions, and the heating conditions are not particularly limited, but in order not to reduce the degree of alignment of the liquid crystal compound, it is more preferably about 120 ° C. or less. preferable.

  It is preferable to fix the molecules of the discotic liquid crystal compound in a hybrid alignment state. The hybrid alignment refers to an alignment state in which the director direction of liquid crystal molecules continuously changes in the layer thickness direction. In addition, Re (550) of the retardation layer is 0 to 70 nm in order for the retardation layer disposed in the cell to contribute to improvement of contrast in the oblique direction and reduction of the color shift in the oblique direction during black display. Rth (550) is preferably about 30 to 300 nm.

  The retardation layer can also be formed using a transfer material. For example, a retardation layer having a desired thickness and desired optical characteristics is formed on a temporary support by the above method, and the retardation layer is transferred onto a substrate surface, for example, a color filter layer. Can do. When the transfer material includes a photosensitive resin layer, a retardation layer divided into fine regions can be formed. In addition, the retardation layer divided into fine regions can also be formed by using an inkjet method, a printing method, or the like. For details, the method described in JP2007-193090A can be referred to.

Further, in the present invention, as shown in FIG. 2, a planarizing layer is formed in a region having a small thickness of the retardation layer, and the difference in thickness from the region having a large thickness is reduced. The entire layer is preferably planarized. A lithography material can be used for forming the planarization layer. Among these, a photoresist material is preferable because it is easy to handle. The following can be illustrated as a preferable photoresist material.
The photoresist material to be used can be appropriately selected according to the required film thickness and processability. For example, for semiconductor materials of Tokyo Ohka Kogyo Co., Ltd., as the photoresist for g-line, OFPR series (standard resist) TSMR series (resist for sub-micron), TCR series as i-line photoresist (high and medium for half-micron) Reflective substrate dye resist), THMR-iP / iN series (half-micron resist), TDMR-AR series (sub-half micron resist), TSQR-iQ series (sub-half micron resist), KrF excimer laser photoresist There are TDUR-P / N series (quarter micron compatible resist) and OEBR series as electron beam photoresist. Moreover, TFR series (high sensitivity positive type for TFT), CFPR series (pigment dispersion negative type for making LCD / PDP color filter), PMER-P series (positive type for STN), TLCR (STN) as photoresists for electronic materials for flat panel displays Positive type), Audil BF series (PDP rib processing dry film resist), and Audil FI series (PDP electrode forming dry film resist). Electronic material photoresists for printed wiring boards / chemical milling include: Odle series (dry film resist), OPSR (photo solder resist), OP resist (negative type for printed wiring boards), TSGR resist (sodium carbonate development type print) There are negative types for wiring boards), PMER (alkaline development negative type / positive type), BMR (plating-resistant negative type), TPR (PVC negative type), EPPR (chemical-resistant negative type), etc. Of course, it is not limited to these.

  An example of a method for forming the planarizing layer with a photoresist material is as follows. First, a photoresist material is applied to the substrate surface. There is no restriction | limiting in particular about the coating method, What is necessary is just the method which can form uniformly thinly. For example, in wet coating, spin coating, gravure coating, (kiss) reverse coating, comma coating, lip coating, capillary (CAP) coating, knife coating, dip coating, curtain coating, As the flow method and the dry coating method, methods such as a vacuum deposition method, a sputtering method, and an ion plating method, a thermal chemical vapor deposition (thermal CVD) method, a plasma CVD method, and the like can be used.

Next, after application, pre-baking and exposure may be performed as necessary, and hardening and / or baking may be performed as necessary.
For exposure, ultraviolet rays (UV including UV-A, UV-B, and UV-C), visible light, gamma rays, X-rays, electron beams, etc., may be irradiated on the entire surface, handling and cost. To ultraviolet (UV) are more preferred.

More specifically, a photoresist is applied to the surface of the substrate, dried, masked with a predetermined pattern plate, closely exposed, developed with water or a developer, and hardened as necessary. Perform membrane treatment and baking treatment.
In an embodiment in which a retardation layer is disposed on a cell substrate using a transfer material, a layer made of a photoresist material is formed in the transfer material, transferred onto the substrate together with the retardation layer, and then exposed and developed. Thus, a planarized layer having a desired thickness can be formed at a desired position.

  The pattern of the mask plate is, for example, a mesh shape, a stripe shape, or a desired pattern. The mesh shape is composed of a plurality of openings or recesses surrounded by line portions, and the shape (mesh pattern) of the openings or recesses is not particularly limited. For example, a triangle such as a regular triangle, a square, a rectangle, or a rhombus A quadrangle such as a trapezoid, a polygon such as a hexagon, a circle, an ellipse, or the like can be applied. A plurality of these openings are combined into a mesh. The stripe shape is composed of a line portion and an opening or a recess between the line portions, and the stripe shape is suitable when an address electrode or the like is provided. In addition, since the desired pattern is determined by how to take out the electrode of the application to be used, it is not a simple geometric pattern, and there are many patterns having complicated shapes, and is not particularly limited. The opening is obtained by removing the photoresist layer, and the recess is obtained by removing the entire thickness of the photoresist layer. Usually, the line width and the line interval (line pitch) are different depending on what is put in the recess, and are in the order of μm to cm, and are not particularly limited.

A chemical reaction chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a visible light halogen lamp, or the like is used as a UV irradiation apparatus (also referred to as a UV lamp) used for UV irradiation. The amount of UV irradiation is preferably such that the integrated energy at a wavelength of 200 to 600 nm is 0.01 to 10 J / cm ² . The UV irradiation atmosphere may be air or an inert gas atmosphere such as nitrogen or argon.
The wavelength of the ultraviolet light is about 200 to 400 nm, and the wavelength may be selected according to the material of the protective layer. The irradiation amount may be irradiated according to the material and amount of the composition, the output of the UV lamp, and the processing speed.

  What is necessary is just to set the thickness of the said flat layer according to the thickness of the phase difference layer formed in a cell, and the order of nm-micrometer is preferable.

The present invention also relates to a TN mode liquid crystal display device having the liquid crystal cell of the present invention. The TN mode liquid crystal display device of the present invention has a TN mode liquid crystal cell having at least one retardation layer therein.
FIG. 4 is a schematic diagram showing the configuration of an example of the TN mode liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 4 includes polarizing plates PL1 and PL2 and a liquid crystal cell LC therebetween. Although the detailed structure of the liquid crystal cell LC is not shown, the liquid crystal cell LC is, for example, the liquid crystal cell LC illustrated in FIG. 3 in which one of the pair of substrates has an in-cell retardation layer on the inner surface. The polarizing plates PL1 and PL2 have polarizers 12 and 14, protective films 16 and 18 on the inner side, and protective films 20 and 22 on the outer side, respectively. The polarizers 12 and 14 are arranged with their respective absorption axes orthogonal to each other. The liquid crystal cell LC is in the TN mode, and when the driving voltage is not supplied to the electrodes, the liquid crystal layer is twisted by about 90 ° and is in a bright display state, and when the driving voltage is supplied to the electrodes, The twisted alignment of the liquid crystal layer is eliminated, and the liquid crystal molecules are aligned with the major axis direction aligned with the direction of the electric field, resulting in a dark display state. The in-cell retardation layer disposed in the liquid crystal cell LC contributes to an improvement in oblique contrast and a reduction in color shift during black display.

In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at a wavelength of λ nm, respectively. Re is measured using KOBRA 21ADH (manufactured by Oji Scientific Instruments) by making light having a wavelength λ nm incident in the normal direction of the film. Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the film with the slow axis in the plane (determined by KOBRA 21ADH) as the tilt axis (rotation axis). A retardation value and a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in the direction, the assumed value of the average refractive index, and the input film thickness value.
Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz. In addition, when the measurement wavelength is not particularly mentioned, the measurement wavelength is 550 nm.

  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.

1. Production of substrate (1) -1 Preparation of Coating Solution 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 coating solution CU-1 for alignment layer.
・ Coating solution composition for thermoplastic resin layer (% by mass)
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

1. -2 Preparation of alignment layer coating liquid AL-1 The following composition was prepared and used as alignment layer coating liquid AL-1.
Composition of alignment film coating solution AL-1 ―――――――――――――――――――――――――――――――――――――
Denatured polyvinyl alcohol 40 parts by weight Water 728 parts by weight Methanol 228 parts by weight Glutaraldehyde (crosslinking agent) 2 parts by weight Citric acid ester (AS3, Sankyo Chemical Co., Ltd.) 0.69 parts by weight ―――――――― ―――――――――――――――――――――――――――――

1. -3 Preparation of Liquid Crystal Composition LC-2 for Forming Retardation Layer A coating liquid LC-2 for a liquid crystal composition for forming a retardation layer having the following composition was prepared.
-Liquid crystal composition LC-2 for forming retardation layer (mass%)
The following discotic liquid crystal compound (1) 41.01
Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4.06
Cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co.) 0.33
Cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 0.11
Fluoroaliphatic group-containing polymer A 0.23 shown below
Fluoroaliphatic group-containing polymer B 0.03 shown below
Photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 1.35
Sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 0.45
Methyl ethyl ketone 131.50

1. -4 Preparation of Coating Solution for Photosensitive Resin Layer A method for preparing a coating solution for the photosensitive resin layer will be described below. Table 1 shows the composition of each coating solution for the photosensitive resin layer.

The compositions in Table 1 are as follows.
・ K pigment dispersion composition (% by mass)
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 (mass%)
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 (mass%)
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 (mass%)
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 (mass%)
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 (mass%)
Benzyl methacrylate / methacrylic acid / methyl methacrylate =
38/25/37 molar ratio random copolymer (weight average molecular weight 30,000) 27.0
Propylene glycol monomethyl ether acetate 73.0

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

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

1. -5 Preparation of Photosensitive Resin Layer Coating Liquid PP-K1 The photosensitive resin layer coating liquid PP-K1 was first weighed in the amounts of K pigment dispersion 1 and propylene glycol monomethyl ether acetate listed in Table 1, and the temperature The mixture was mixed at 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [ 4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and Megafac F-176PF Surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.). It was obtained by stirring at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

1. -6 Preparation of Coating Solution PP-R1 for Photosensitive Resin Layer Coating solution PP-R1 for photosensitive resin layer was prepared by first preparing R pigment dispersion 1, R pigment dispersion 2, propylene glycol monomethyl ether in the amounts shown in Table 1. The acetate is weighed out, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p -Styrylstyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine Phenothiazine was added in this order at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then the amount of ED152 shown in Table 1 was weighed and heated. Mix at 24 ° C. (± 2 ° C.), stir at 150 rpm for 20 minutes, and then weigh out the amount of Megafac F-176PF surfactant 1 listed in Table 1 and add at a temperature of 24 ° C. (± 2 ° C.). It was obtained by stirring at 30 rpm for 30 minutes and filtering through nylon mesh # 200.

1. -7 Preparation of photosensitive resin layer coating solution PP-G1 The photosensitive resin layer coating solution PP-G1 was first prepared by measuring the amounts of G pigment dispersion, CF Yellow EX3393, and propylene glycol monomethyl ether acetate listed in Table 1. And mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) listed in Table 1 ) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine, phenothiazine. Weigh out and add in this order at a temperature of 24 ° C. (± 2 ° C.) and stir at 150 rpm for 30 minutes. Tsu weighed click F-176PF surfactant 1, and stirred 30rpm5 minutes was added at a temperature 24 ℃ (± 2 ℃), was obtained by filtering with a nylon mesh # 200.

1. -8 Preparation of photosensitive resin layer coating solution PP-B1 The photosensitive resin layer coating solution PP-B1 was first weighed in the amounts of CF Blue EX3357, CF Blue EX3383, and propylene glycol monomethyl ether acetate listed in Table 1. , Mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1 listed in Table 1 , 3,4-oxadiazole and phenothiazine were 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. Weigh out the amount of MegaFuck F-176PF Surfactant 1 and add it at a temperature of 24 ° C (± 2 ° C) and stir at 30 rpm for 5 minutes. Obtained by filtering through mesh # 200.

1. -9 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 .

1. -10 Production of transfer material for production of light-shielding partition wall Each substance in Table 2 was placed in a stirring autoclave substituted with nitrogen gas, polymerization temperature 50 ° C, polymerization pressure 5 atm (pressure with butadiene), polymerization time 20 hours. Then, emulsion polymerization or the like was performed, and the remaining monomer (about 5% of the monomer) was removed by distillation to obtain a latex having a dry solid content of 49%.

A coating solution having the following composition was applied to a 75 um thick polyethylene terephthalate (PET) film biaxially stretched and oriented and crystallized at a rate of 20 mL per m ^{2 and} dried at 120 ° C. for 10 minutes to provide a temporary support. A was obtained.
-Temporary support A forming coating solution composition 100 parts by weight of the latex 2,4-dichloro-6-hydroxy-1,3,5-triazine Na salt 0.14 parts by weight Water 2500 parts by weight

  On the temporary support A, the photosensitive resin composition PP-K1 is applied and dried to form a 2.3 μm thick black photosensitive resin layer, and a 75 μm thick PET film is laminated thereon at 110 ° C. As a temporary support B, a transfer material K-1 for producing a light-shielding partition was produced.

1. -11 Production of photosensitive resin transfer material for RGB On a polyethylene terephthalate 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. The film thickness of the thermoplastic resin layer was 14.6 μm. Next, the temporary support was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried (saponification treatment). The surface energy of this film was determined by a contact angle method and found to be 62 mN / m.
On this temporary support, the alignment layer coating liquid AL-1 was applied at 24 mL / m ² with a # 14 wire bar coater and dried with warm air at 100 ° C. for 120 seconds to form an alignment layer.
Subsequently, the formed alignment layer was rubbed. The orientation of the polyethylene terephthalate film transported at 30 m / min by rotating the # 3.2 wire bar in the same direction as the film transport direction by rotating the # 3.2 wire bar at 1,171 rotations. The film was continuously applied to the rubbing surface of the film.
Thereafter, the solvent is dried by continuously heating from room temperature to 100 ° C., and in the drying zone at 135 ° C., the film surface wind speed corresponding to the coating layer is 1.5 m / sec in parallel with the film transport direction. For about 120 seconds to align the discotic liquid crystal compound.
Next, ultraviolet rays with an illuminance of 600 mW were irradiated for 4 seconds with a high-pressure mercury lamp (ultraviolet lamp: output 160 W / cm, emission length 1.6 m), the crosslinking reaction was advanced, and the discotic liquid crystal compound was fixed in the alignment state. Thereafter, the mixture was allowed to cool to room temperature to form a retardation layer having a thickness of 1.37 μm. Finally, photosensitive resin composition PP-B1 was applied and dried to prepare photosensitive resin transfer material B-1 for B.
G and R photosensitive resin transfer for G and R, respectively, except that the thickness was adjusted to 1.64 μm by changing the amount of methyl ethyl ketone in LC-2 to 102.00 parts by mass. Materials G-1 and R-1 were formed.

1. -12 Retardation measurement When the polarizing plate was placed in a crossed Nicol configuration and the unevenness of the retardation layer formed on the temporary support was observed, the unevenness was found even when viewed from the front and the direction inclined 60 ° from the normal. Not detected.
Further, the retardation of each of the retardation layers of the R photosensitive transfer material R-1, the G photosensitive transfer material G-1, and the B photosensitive transfer material B-1 was measured. . Re (550) of the retardation layer of the photosensitive transfer material for G: 51.1 nm
Re (630) of retardation layer of photosensitive transfer material for R: 47.6 nm
Re (450) of retardation layer of photosensitive transfer material for B: 50.8 nm

1. -13 Preparation of color filter and formation of black (K) image A non-alkali glass substrate serving as a support was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower, After washing with pure water shower, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% aqueous solution, trade name: KBM603, Shin-Etsu Chemical) is sprayed for 20 seconds with a shower, and pure water shower is washed. did. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating apparatus.
After peeling off the temporary support A of the photosensitive resin transfer material K-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) Lamination was performed at 130 ° C., linear pressure of 100 N / cm, and conveyance speed of 2.2 m / min.
After peeling off the temporary support B, exposure is performed with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask having an image pattern) standing vertically. The distance between the mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Film Co., Ltd.), 30 Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Subsequently, sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T- Using CD1, manufactured by Fuji Film Co., Ltd., shower development was performed at a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterned pixel.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name "T-SD1 (manufactured by FUJIFILM Corporation)" was used and a shower was performed at a cone type nozzle pressure of 0.02 MPa. Then, the residue was removed with a rotating brush having nylon bristles to obtain a black (K) image, and then the substrate was further post-irradiated with 500 mJ / cm ² light from the resin layer side with an ultra-high pressure mercury lamp. After the 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. After pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes by a substrate preheating device without using a silane coupling solution.

-Red (R) pixel formation After peeling off the protective film of the photosensitive resin transfer material R-1, the black (K) image is formed using a laminator (manufactured by Hitachi Industries (Lamic II type)). Then, it was laminated on a substrate heated at 100 ° C. for 2 minutes at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After peeling off the temporary support, the distance between the exposure mask surface and the photosensitive resin layer is set to 40 μm with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount is set to 500 mJ. / Cm ^{2 to} 1000 mJ / cm ² , and exposure was performed to prepare a sample in which the formed colored layer and the optically anisotropic layer pattern were laminated stepwise.
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Film Co., Ltd.), 30 Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Subsequently, sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Film Co., Ltd.) and 2-propanol mixed solution (mixing ratio 4: 1), while developing the shower at a cone type nozzle pressure of 0.15 MPa, the development residue on the surface was removed with a rotating brush. . In this step, the optically anisotropic layer and the photosensitive resin layer were developed to obtain a patterned pixel in which the end face of the optically anisotropic layer pattern was inside the end face of the colored layer (R portion).
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name "T-SD1 (manufactured by FUJIFILM Corporation)" was used and a shower was performed at a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a rotating brush having nylon bristles, and after development, baking was performed in an electric furnace for 120 minutes in an air atmosphere at a temperature of 200 ° C. to 250 ° C.

-Formation of Green (G) Pixel Using the photosensitive resin transfer material G-1, a green (G) pixel is formed on the substrate on which the red (R) pixel is formed in the same process as the photosensitive resin transfer material R-1. G) pixel was obtained.

Formation of blue (B) pixels Blue (B) pixels are formed in the same process on the substrate on which the red (R) pixels and green (G) pixels are formed using the photosensitive resin transfer material B-1. Got. The substrate on which the R, G, and B pixels were formed was again washed with a brush as described above, washed with pure water shower, and then heated at 100 ° C. for 2 minutes with a substrate heating device to produce a target color filter.

1. -14 Formation of transparent electrode A transparent electrode film was formed on the produced color filter by sputtering of ITO.

1. -15 Formation of alignment layer Further, an alignment layer was provided thereon. As the alignment material, JSR polyimide JALS204 was used, and was selectively applied to the region where the pixel electrodes were arranged by a roll coating method. After coating, prebaking was performed in an atmosphere at 80 ° C. for 15 minutes, and baking was further performed at 200 ° C. for 60 minutes. As a result, an alignment layer having a thickness of about 0.5 μm was obtained.

  As described above, a substrate (1) having a color filter layer and a retardation layer was produced.

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

2. -2 Preparation of alignment layer coating liquid AL-1 The following composition was prepared and used as alignment layer coating liquid AL-1.
Composition of alignment film coating solution AL-1 ―――――――――――――――――――――――――――――――――――――
Denatured polyvinyl alcohol 40 parts by weight Water 728 parts by weight Methanol 228 parts by weight Glutaraldehyde (crosslinking agent) 2 parts by weight Citric acid ester (AS3, Sankyo Chemical Co., Ltd.) 0.69 parts by weight ―――――――― ―――――――――――――――――――――――――――――

2. -3 Preparation of Liquid Crystal Composition LC-2 for Forming Retardation Layer A coating liquid LC-2 for a liquid crystal composition for forming a retardation layer having the following composition was prepared.
―――――――――――――――――――――――――――――――――――――
The following discotic liquid crystal compound (1) 41.01 parts by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4.06 parts by mass cellulose acetate butyrate (CAB551-0.2) 0.33 parts by mass cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 0.11 parts by mass The following fluoroaliphatic group-containing polymer A 0.23 parts by mass Fluoroaliphatic group-containing polymer B 0.03 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 1.35 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.45 Parts by mass methyl ethyl ketone 117.00 parts by mass ―――――――――――――――――― ------------------

2. -4 Production of photosensitive resin transfer material for B Using a slit-like nozzle, a thermoplastic resin layer coating solution CU-1 is applied onto a 75 μm-thick polyethylene terephthalate film temporary support and dried to be thermoplastic. A resin layer was formed. The film thickness was 14.6 μm.
Next, the temporary support was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried (saponification treatment). The surface energy of this film was determined by a contact angle method and found to be 62 mN / m.
On this temporary support, the alignment layer coating solution AL-1 was applied at 24 mL / m ² with a # 14 wire bar coater and dried with warm air at 100 ° C. for 120 seconds to form an alignment layer.
Subsequently, the formed alignment layer was rubbed. Then, the polyethylene terephthalate film transported at 30 m / min by rotating the coating liquid LC-2 for retardation layer in the same direction as the film transport direction by rotating the # 3.2 wire bar at 1,171 rotations. The alignment layer was rubbed continuously on the surface to be rubbed.
Thereafter, the solvent is dried by continuously heating from room temperature to 100 ° C., and in the drying zone at 135 ° C., the film surface wind speed corresponding to the coating layer is 1.5 m / sec in parallel with the film transport direction. For about 120 seconds to align the discotic liquid crystal compound in the coating layer.
Next, ultraviolet rays with an illuminance of 600 mW were irradiated for 4 seconds with a high-pressure mercury lamp (ultraviolet lamp: output 160 W / cm, emission length 1.6 m), the crosslinking reaction was advanced, and the discotic liquid crystal compound was fixed in the alignment state. Thereafter, the mixture was allowed to cool to room temperature to form a retardation layer having a thickness of 1.48 μm.
Finally, a resist solution (CFPR CL-016S) manufactured by Tokyo Ohka Co., Ltd., which is a photoresist material, was spin-coated and baked at 120 ° C. for 30 minutes to obtain a uniform resist film having a thickness of 0.26 μm. In this way, a photosensitive resin transfer material B-1 for B was produced.

2. -5 Production of photosensitive resin transfer material for R and G On a 75 μm thick polyethylene terephthalate film temporary support, coating liquid CU-1 for thermoplastic resin layer was applied using a slit nozzle and dried. Thus, a thermoplastic resin layer was formed. The thickness of this layer was 14.6 μm.
Next, the temporary support was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, neutralized with sulfuric acid, washed with pure water and dried (saponification treatment). The surface energy of this film was determined by a contact angle method and found to be 62 mN / m.
On this temporary support, the alignment layer coating liquid AL-1 was applied at 24 mL / m ² with a # 14 wire bar coater and dried with warm air at 100 ° C. for 120 seconds to form an alignment layer.
Subsequently, the formed alignment layer was rubbed. The coating liquid LC-2 for retardation layer prepared by changing the amount of methyl ethyl ketone to 102.00 parts by mass was rotated in the same direction as the film transport direction by rotating the # 3.2 wire bar by 1,171 rotations. Then, it was continuously applied to the rubbing-treated surface of the alignment film of the polyethylene terephthalate film transported at 30 m / min.
Thereafter, the solvent is dried by continuously heating from room temperature to 100 ° C., and in the drying zone at 135 ° C., the film surface wind speed corresponding to the coating layer is 1.5 m / sec in parallel with the film transport direction. For about 120 seconds to align the discotic liquid crystal compound.
Next, ultraviolet rays with an illuminance of 600 mW were irradiated for 4 seconds with a high-pressure mercury lamp (ultraviolet lamp: output 160 W / cm, emission length 1.6 m), the crosslinking reaction was advanced, and the discotic liquid crystal compound was fixed in the alignment state. Thereafter, it was allowed to cool to room temperature to form a retardation layer having a thickness of 1.64 μm.
Finally, a resist solution (CFPR CL-016S) manufactured by Tokyo Ohka Co., Ltd., which is a photoresist material, was spin-coated and baked at 120 ° C. for 30 minutes to obtain a uniform resist film having a thickness of 0.10 μm. In this way, R photosensitive resin transfer material R-1 was produced.
The photosensitive resin transfer material G-1 for G was produced in the same manner as the photosensitive resin transfer material R-1 for R. The thickness of the retardation layer in the photosensitive resin transfer material G-1 for G was also 1.64 μm.

2. -6 Retardation measurement When the polarizing plate was placed in a crossed Nicol arrangement and the unevenness of the retardation layer formed on the temporary support was observed, the unevenness was found even when viewed from the front and the direction inclined 60 ° from the normal. Not detected.
Further, the retardation of each of the retardation layers of the R photosensitive transfer material R-1, the G photosensitive transfer material G-1, and the B photosensitive transfer material B-1 was measured. . Re (550) of the retardation layer of the photosensitive transfer material for G: 51.1 nm
Re (630) of retardation layer of photosensitive transfer material for R: 47.6 nm
Re (450) of the retardation layer of the photosensitive transfer material for B: 54.8 nm
The measurement light was unified to a wavelength of 550 nm as follows.
Re (550) of the retardation layer of the photosensitive transfer material for G: 51.1 nm
Re (550) of retardation layer of photosensitive transfer material for R: 51.1 nm
Re (550) of retardation layer of photosensitive transfer material for B: 46.2 nm

2. -7 Formation of red (R) retardation layer An 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 with a shower, and after pure water shower washing, A silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% aqueous solution, trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating apparatus.
The produced photosensitive resin transfer material R-1 was heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), with a rubber roller temperature of 130 ° C. and a linear pressure of 100 N. / Cm, laminating at a conveyance speed of 1.4 m / min.
After peeling off the temporary support, patterning mask is used, the exposure time is adjusted and irradiated, and then it is immersed in a developer (N-A3K manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 1 minute at room temperature (photolithographic method) The pattern shape was a stripe having a width of 0.094 mm and a pitch of 0.282 mm and perpendicular to the bottom of the substrate). A laminate of the flat layer and the retardation layer was formed only in a region corresponding to the R layer of the color filter.
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Film Co., Ltd.), 30 Shower development was performed at 50 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name "T-SD1 (manufactured by FUJIFILM Corporation)" was used and a shower was performed at a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a rotating brush having nylon bristles, and after development, baking was performed in an electric furnace for 120 minutes in an air atmosphere at a temperature of 200 ° C. to 250 ° C.

2. -8 Formation of retardation layer for green (G) On the substrate on which the retardation layer for red (R) is formed using the produced photosensitive resin transfer material G-1, the same as the photosensitive resin transfer material R-1 In this step, a retardation layer for green (G) was formed.

2. -9 Formation of a retardation layer for blue (B) On the substrate on which the retardation layer for red (R) and the retardation layer for green (G) are formed using the photosensitive resin transfer material B-1. A blue (B) retardation layer was formed in the same process as the formation of the red (R) retardation layer. The substrate on which the R, G, and B retardation layers 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 to obtain a target substrate. Produced.

2. -10 Formation of transparent electrode A transparent electrode film was formed on the substrate prepared above by sputtering of ITO.
On the common electrode formed of this transparent conductive film, an electrode having an alignment layer was prepared.
2. -11 Formation of opposite alignment layer A polyimide alignment layer was formed on the transparent conductive layer. As the alignment material, JSR polyimide JALS204 was used, and was selectively applied to the region where the pixel electrodes were arranged by a roll coating method. After coating, prebaking was performed in an atmosphere at 80 ° C. for 15 minutes, and baking was further performed at 200 ° C. for 60 minutes. As a result, an alignment layer having a thickness of about 0.5 μm was obtained.

  Thus, the board | substrate (2) which has a planarization layer and a phase difference layer was produced.

3. Preparation of liquid crystal cell As a substrate (3), an RGB color filter layer, a common electrode formed of a transparent conductive film, and an alignment layer formed thereon were prepared. The alignment layer was rubbed.
As the substrate (4), a substrate in which an alignment layer was formed on a common electrode formed of a transparent conductive film was prepared. The alignment layer was rubbed.
As the substrate (5), the amount of methyl ethyl ketone in LC-2 used in the production of the photosensitive resin transfer material for RGB is 102.00 parts by mass for G for R, and 117 for B. It was produced in the same manner as the substrate (1) except that the amount was 0.000 part by mass. The retardation of each of the retardation layers of the R photosensitive transfer material R-1, the G photosensitive transfer material G-1, and the B photosensitive transfer material B-1 was measured.
Re (550) of the retardation layer of the photosensitive transfer material for G: 51.1 nm
Re (630) of retardation layer of photosensitive transfer material for R: 47.6 nm
Re (450) of the retardation layer of the photosensitive transfer material for B: 54.8 nm
Two substrates (substrate (1), substrate (3) or substrate (5) and substrate (2) or (4)) were stacked with the alignment film facing each other through a 4.1 μm spacer. The orientation of the substrate was adjusted so that the rubbing directions of the alignment film were orthogonal. A rod-like liquid crystal molecule (ZL4792, manufactured by Merck & Co., Inc.) was injected into the gap between the substrates to form a liquid crystal layer. The Δn of the liquid crystal molecule was 0.0969.
A seal pattern is formed around the substrate. An epoxy resin containing 1% by mass of spacer particles (Strectbond XN-21S manufactured by Nissan Chemical Industries) was printed with a seal dispenser device in a form in which a portion corresponding to the liquid crystal injection port was opened in a predetermined area surrounding the display area. This was calcined at 80 ° C. for 30 minutes.

  In this way, the liquid crystal cell 1 (Example 1) using the substrate (1) as the display surface side liquid crystal cell substrate and the substrate (4) as the backlight side liquid crystal cell substrate, and the substrate ( 5), and a liquid crystal cell 2 (Example 2) using the substrate (2) as the backlight side liquid crystal cell substrate, a substrate (3) as the display surface side liquid crystal cell substrate, and a substrate ( A liquid crystal cell 3 (Comparative Example) using 4) was prepared.

4). 3. Production and evaluation of TN mode liquid crystal display device -1 Production of polarizing plate 1 (Production of cellulose acetate film: TAC-1)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
・ Cellulose acetate solution composition ――――――――――――――――――――――――――――――――――――――
Cellulose acetate having an acetylation degree of 60.7 to 61.1% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 336 parts by mass Methanol (second solvent) 29 parts by mass 1-butanol (third solvent) 11 parts by mass ――――――――――――――――――――――――――― ――――――――――

  In another mixing tank, 16 parts by mass of the following retardation increasing agent 1, 92 parts by mass of methylene chloride and 8 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution. A dope was prepared by mixing 31 parts by mass of the retardation increasing agent solution with 487.7 parts by mass of the cellulose acetate solution and stirring sufficiently.

  The obtained dope was cast using a band stretching machine. After the film surface temperature on the band reached 40 ° C., the film was dried with warm air of 70 ° C. for 1 minute, the film was peeled off from the band, and dried with 140 ° C. drying air for 10 minutes. A 3% by mass cellulose acetate film (TAC-1) (thickness: 80 μm) was produced. The optical properties of the produced cellulose acetate film (TAC-1) were Re = 4 nm and Rth = 97 nm (measured at a wavelength of 550 nm).

  The prepared TAC-1 was immersed in a 2.0N potassium hydroxide solution (25 ° C.) for 2 minutes, then neutralized with sulfuric acid, washed with pure water and dried. The surface energy of this film was determined by a contact angle method and found to be 62 mN / m.

A polyvinyl alcohol (PVA) film having a thickness of 80 μm is dyed by immersing it in an aqueous iodine solution having an iodine concentration of 0.05% by mass at 30 ° C. for 60 seconds, and then in an aqueous boric acid solution having a boric acid concentration of 4% by mass. The film was vertically stretched to 5 times the original length while being immersed for 2 seconds, and then dried at 50 ° C. for 4 minutes to obtain a polarizing film having a thickness of 20 μm.
A commercially available cellulose acetate film was immersed in an aqueous sodium hydroxide solution at 55 ° C. at 1.5 mol / L, and then the sodium hydroxide was sufficiently washed away with water. Then, after being immersed in a diluted sulfuric acid aqueous solution at 35 ° C. for 1 minute at 0.005 mol / L, the diluted sulfuric acid aqueous solution was sufficiently washed away by immersion in water. Finally, the sample was thoroughly dried at 120 ° C.
A polarizing plate 1 was obtained by sandwiching a polarizing film between TAC-1 produced as described above and a commercially available cellulose acetate film subjected to saponification treatment, and using a polyvinyl alcohol-based adhesive. Fujitac TF80UL (Fuji Film Co., Ltd.) was used as a commercially available cellulose acetate film. At this time, since the polarizing film and the protective films on both sides of the polarizing film are produced in a roll form, the longitudinal directions of the roll films are parallel to each other and are continuously bonded. Therefore, the roll longitudinal direction of the optical compensation film and the polarizer absorption axis were parallel to each other.

4). -2 Production of Polarizing Plate 2 On the saponified TAC-1 used in the production of the polarizing plate 1, a coating solution having the following composition was applied at 24 mL / m ² with a # 14 wire bar coater and heated at 100 ° C. Dry with wind for 120 seconds. Next, the longitudinal direction of TAC-1 was set to 0 degree, and the formed film was rubbed in the 0 degree direction.
・ Alignment film coating solution composition ――――――――――――――――――――――――――――――――――――――
Denatured polyvinyl alcohol 40 parts by weight Water 728 parts by weight Methanol 228 parts by weight Glutaraldehyde (crosslinking agent) 2 parts by weight Citric acid ester (AS3, Sankyo Chemical Co., Ltd.) 0.69 parts by weight ―――――――― ―――――――――――――――――――――――――――――

-Preparation of liquid crystal composition for forming optically anisotropic layer A coating liquid for a liquid crystal composition for forming an optically anisotropic layer having the following composition was prepared.
―――――――――――――――――――――――――――――――――――――
The following discotic liquid crystal compound (1) 41.01 parts by mass Ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4.06 parts by mass cellulose acetate butyrate (CAB551-0.2) 0.33 parts by mass cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 0.11 parts by mass The following fluoroaliphatic group-containing polymer A 0.23 parts by mass Fluoroaliphatic group-containing polymer B 0.03 parts by mass photopolymerization initiator (Irgacure 907, manufactured by Ciba Japan) 1.35 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.45 Part by weight Methyl ethyl ketone 102.00 parts by weight ―――――――――――――――――― ------------------

-Formation of optically anisotropic layer The liquid crystal composition for forming the optically anisotropic layer is conveyed at 30 m / min by rotating the wire bar # 3.2 in the same direction as the film conveying direction at 1,171 rotations. It was continuously applied to the alignment film surface of the roll film.
Thereafter, in the step of continuously heating from room temperature to 100 ° C., the solvent is dried, and then in the drying zone at 135 ° C., the film surface wind speed corresponding to the discotic liquid crystalline compound layer is 1.5 m parallel to the film conveying direction. / Sec and heated for about 120 seconds to align the discotic liquid crystalline compound.
Next, ultraviolet rays with an illuminance of 600 mW were irradiated for 4 seconds with a high-pressure mercury lamp (ultraviolet lamp: output 160 W / cm, emission length 1.6 m), the crosslinking reaction was advanced, and the discotic liquid crystalline compound was fixed in the orientation. Thereafter, the film was allowed to cool to room temperature and wound into a cylindrical shape to form a roll, thereby producing an optical compensation film.

-Production of Polarizing Plate 2 A polyvinyl alcohol (PVA) film having a thickness of 80 µm was dyed by immersing it in an iodine aqueous solution having an iodine concentration of 0.05% by mass at 30 ° C for 60 seconds, and then having a boric acid concentration of 4% by mass. While being immersed in an aqueous boric acid solution for 60 seconds, the film was longitudinally stretched 5 times the original length and then dried at 50 ° C. for 4 minutes to obtain a polarizing film having a thickness of 20 μm.
A commercially available cellulose acetate film was immersed in an aqueous sodium hydroxide solution at 55 ° C. at 1.5 mol / L, and then the sodium hydroxide was sufficiently washed away with water. Then, after being immersed in a diluted sulfuric acid aqueous solution at 35 ° C. for 1 minute at 0.005 mol / L, the diluted sulfuric acid aqueous solution was sufficiently washed away by immersion in water. Finally, the sample was thoroughly dried at 120 ° C.
A polarizing plate 2 was obtained by combining the optical compensation film produced as described above and a commercially available cellulose acetate film subjected to a saponification treatment, and sandwiching the polarizing film with a polyvinyl alcohol adhesive. . Here, the optical compensation film was bonded with the liquid crystal compound layer outside. As a commercially available cellulose acetate film, Fujitac TF80UL (manufactured by FUJIFILM Corporation) was used. At this time, since the polarizing film and the protective films on both sides of the polarizing film are produced in a roll form, the longitudinal directions of the roll films are parallel to each other and are continuously bonded. Therefore, the roll longitudinal direction of the optical compensation film and the polarizer absorption axis were parallel to each other.

4). -3 Production of TN mode liquid crystal display device 1 (Example 1) The polarizing plate 1 is placed on the outer surface of the liquid crystal cell substrate on the CF side (display surface side) of the TN mode liquid crystal cell 1 produced as described above. 1 was attached to face the substrate. A polarizing plate 2 was attached to the outside of the substrate on the backlight side with the surface of the liquid crystal compound layer facing the substrate. In this manner, a TN mode liquid crystal display device 1 was produced. The absorption axes of the polarizing plates 1 and 2 and the rubbing direction applied to the attached substrate were arranged to be orthogonal to each other.

4). -4 Production of TN mode liquid crystal display device 2 (Example 2) On the outer surface of the liquid crystal cell substrate on the CF side (display surface side) of the TN mode liquid crystal cell 2 produced as described above, and on the outside of the substrate on the backlight side The polarizing plate 1 was pasted with the TAC-1 facing the substrate. In this way, a TN mode liquid crystal display device 2 was produced. The absorption axes of both polarizing plates 1 and the direction of rubbing applied to the attached substrate were arranged to be orthogonal to each other.

4). -5 Production of TN mode liquid crystal display device 3 (comparative example) On the outer surface of the liquid crystal cell substrate on the CF side (display surface side) of the TN mode liquid crystal cell 3 produced as described above and on the outer side of the substrate on the backlight side, The polarizing plate 2 was attached with the surface of the liquid crystal compound layer facing the substrate. In this way, a TN mode liquid crystal display device 3 was produced. The absorption axis of the polarizing plate 2 and the rubbing direction applied to the attached substrate were arranged to be orthogonal to each other.

4). -6 Evaluation For each of the produced TN mode liquid crystal display devices 1 to 3, the contrast in the oblique direction (direction of azimuth angle 90 ° and polar angle 50 °) and the normal direction and the oblique direction with respect to the display surface during black display ( Color shift values (Δu′v ′) with respect to an azimuth angle of 90 ° and a polar angle of 50 ° were measured. The results are shown in the table below.

It is a cross-sectional schematic diagram of an example of the liquid crystal cell substrate which can be used for this invention. It is a cross-sectional schematic diagram of an example of the liquid crystal cell substrate which can be used for this invention. It is a cross-sectional schematic diagram of an example of the TN mode liquid crystal cell of this invention. It is a cross-sectional schematic diagram of an example of the TN mode liquid crystal display device of this invention.

Explanation of symbols

1 Substrate 2 Shading layer (black matrix)
3, 3 'colored layer (color filter layer)
3R, 3'R Red layer 3G, 3'G Green layer 3B, 3'B Blue layer 4, 4 'In-cell optical compensation layer 4r, 4'r In-cell optical compensation layer region 4g, 4' corresponding to red layer 'g In-cell optical compensation layer region 4b, 4'b corresponding to green layer In-cell optical compensation layer region 5 corresponding to blue layer Transparent electrode layer 6b, 6g Planarizing layer 7 Alignment layer 8 Liquid crystal layer 12, 14 Polarizers 16, 18, 20, 22 Protective film LC Liquid crystal cell PL1 Polarizing plate PL2 Polarizing plate S1 Display surface side liquid crystal cell substrate S2 Backlight side liquid crystal cell substrate

Claims (7)

A pair of substrates;
A liquid crystal layer disposed between the pair of substrates;
A color filter layer comprising a plurality of colored layers having different hues disposed on at least one inner surface of the pair of substrates;
A retardation layer disposed in a region corresponding to the colored layer of the color filter layer, which is an inner surface of the substrate having the color filter layer or the other substrate,
The TN mode liquid crystal cell, wherein the retardation layer contains a discotic liquid crystal compound fixed in an aligned state, and the optical characteristics thereof are different between regions depending on the hue of the corresponding colored layer . 2. The TN mode liquid crystal cell according to claim 1, wherein among the plurality of colored layers of the color filter layer, at least two colored layers having different hues have different thicknesses. The color filter layer includes a red (R) layer, a green (G) layer, and a blue (B) layer, and at least the thickness of the B layer is larger than the thickness of the R layer and the G layer, whereby the B layer 3. The TN mode liquid crystal cell according to claim 2, wherein a thickness of the region of the liquid crystal layer corresponding to is smaller than a region of the liquid crystal layer corresponding to the R layer and the G layer. The thickness of the retardation layer varies between a plurality of regions of the retardation layer according to the hue of the corresponding coloring layer, whereby the in-plane retardation Re of the retardation layer corresponds to the corresponding coloring layer. 4. The TN mode liquid crystal cell according to claim 1, wherein the TN mode liquid crystal cell is different from each other in a plurality of regions according to the hue. The color filter layer includes a red (R) layer, a green (G) layer, and a blue (B) layer, and a thickness of a region corresponding to the B layer of the retardation layer corresponds to the R layer and the G layer. The TN mode liquid crystal cell according to claim 4, wherein the TN mode liquid crystal cell is smaller than the thickness of the region. The TN mode liquid crystal cell according to claim 1, wherein the retardation layer is provided on each of the inner surfaces of the pair of substrates. A TN mode liquid crystal display device comprising the liquid crystal cell according to claim 1.

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