JP2007193088A - Method for fabricating substrate for liquid crystal cell and liquid crystal cell, liquid crystal cel, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of simply and stably fabricating a substrate for liquid crystal cell having an alignment control structure and optical compensability. <P>SOLUTION: In the method for manufacturing the substrate for liquid crystal cell having alignment control grooves, an optically anisotropic layer transferred from a transfer material is formed on the surface of a transparent substrate, simultaneously or thereafter groove shaped lacking sections are provided on the optically anisotropic layer, thereby using the lacking sections as the alignment control grooves. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid crystal cell substrate and a novel method for producing a liquid crystal cell. The present invention also relates to a liquid crystal cell and a liquid crystal display device manufactured using such a method.

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

  In order to improve this viewing angle characteristic, an optically anisotropic layer (optical compensation sheet) for viewing angle compensation has been used. Until now, LCDs having excellent contrast viewing angle characteristics have been proposed by using optical compensation sheets having various optical characteristics for the various display modes described above. In particular, the three modes of OCB, VA, and IPS have wide viewing angle characteristics in all directions as wide viewing angle modes, and are already widely used in televisions for home use.

In these liquid crystal cells, the optical compensation sheet is usually bonded to a polarizing plate and provided outside the liquid crystal cell with an adhesive.
However, the conventional technology has the following problems.
First, when a polarizing plate with a phase difference is placed outside the liquid crystal cell, the required attaching accuracy is strict, especially in large-sized ones, and the attaching process is stable due to warpage and misalignment. May not be possible. As a result, an expensive polarizing plate with a retardation plate is wasted, causing a cost increase. Further, during the operation of the liquid crystal panel, the attached retardation plate is subjected to stress due to expansion and contraction of the polarizing plate support due to heat from the backlight or the like, and the optical characteristics are changed. In this case, the phase compensation effect of the phase difference plate is insufficient at the deformed portion, and light leakage occurs in a black state. Such a phenomenon occurs more significantly as the size of the liquid crystal panel increases. That is, as the size of the liquid crystal panel is increased, the polarizing plate is also increased and the amount of contraction and expansion is increased, so that the amount of deformation of the polarizing plate support is increased, and a white-out state is remarkably generated.

  As described above, the prior art has a yield problem associated with the accuracy of attaching to the outside of the liquid crystal cell and a light leakage problem associated with the expansion and contraction of the polarizing plate support.

On the other hand, the technique which provides an optically anisotropic layer inside a liquid crystal cell instead of sticking an optically anisotropic layer and a polarizing plate on a liquid crystal cell is proposed (patent document 1). Furthermore, a technique has been proposed in which an optically anisotropic layer is formed in a liquid crystal cell and the optically anisotropic layer is used as a liquid crystal layer alignment control structure (see Patent Document 2).
However, it is difficult to form an optically anisotropic layer having optically uniform optical anisotropy characteristics in a liquid crystal cell, and since the optically anisotropic layer is provided inside the liquid crystal cell, it is manufactured. There was a problem that the number of processes increased and cost feasibility was poor.
JP 2004-240102 A JP 2000-221506 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method capable of easily and stably producing a liquid crystal cell substrate having an alignment control structure and an optical compensation capability. Another object of the present invention is to provide a method capable of easily and stably producing a liquid crystal cell having an optically anisotropic layer in the cell. Another object of the present invention is to provide a liquid crystal cell and a liquid crystal display device in which light leakage is reduced and viewing angle characteristics are improved.

  As a result of intensive studies for solving the above problems, the inventors of the present invention can easily and stably form an optically anisotropic layer divided into a plurality of regions using a transfer material. The inventors have obtained the knowledge that both the liquid crystal alignment function and the optical compensation function can be simultaneously imparted to the substrate, and further studies have been made based on this knowledge to complete the present invention.

Means for solving the above problems are as follows.
[1] A method for producing a substrate for a liquid crystal cell having an alignment control groove,
At the same time as or after forming the optically anisotropic layer transferred from the transfer material on the surface of the transparent substrate, a groove-like missing part is provided in the optically anisotropic layer, and the orientational control is performed on the missing part. The manufacturing method of the board | substrate for liquid crystal cells including making it into a groove | channel.
[2] The method according to [1], wherein a depth of the groove-like missing portion is 0.2 to 5.0 μm.
[3] The method according to [1] or [2], wherein side surfaces constituting the groove-like missing portion are inclined at a predetermined angle.
[4] The method according to any one of [1] to [3], wherein the groove-like missing portion is formed by pattern exposure and development.
[5] The method according to [4], wherein the transfer material has at least one optically anisotropic layer and at least one photosensitive resin layer on a temporary support.
[6] The method according to any one of [1] to [5], further comprising forming a transparent electrode film on the optically anisotropic layer.
[7] A step of producing a first substrate that forms an alignment control groove by providing a groove-like missing portion at the same time or after the optical anisotropic layer transferred from the transfer material is formed on the surface of the transparent substrate. When,
Placing the first substrate opposite the second substrate with the surface on which the orientation control groove is formed facing inside;
And a step of injecting liquid crystal between the first and second substrates arranged to face each other to form a liquid crystal layer.
[8] The method further includes a step of forming a concave portion or a convex portion on a surface of the second substrate facing the first substrate at a position corresponding to the orientation control groove formed in the first substrate. 7].
[9] A liquid crystal cell substrate produced by any one of the methods [1] to [8].
[10] A liquid crystal cell having first and second substrates and a liquid crystal layer sandwiched between the first and second substrates, wherein at least the first substrate is for the liquid crystal cell according to [9]. A liquid crystal cell, which is a substrate and is disposed with the surface on which the alignment control groove is formed facing the liquid crystal layer.
[11] The liquid crystal cell according to [10], wherein the second substrate has a concave portion on a surface facing the first substrate at a position corresponding to the alignment control groove formed in the first substrate.
[12] The liquid crystal cell according to [11], wherein the second substrate has a transparent electrode film on a surface facing the first substrate, and the concave portion is a slit formed in the transparent electrode film.
[13] The liquid crystal cell according to [10], wherein the second substrate has a convex portion on a surface facing the first substrate at a position corresponding to an alignment control groove formed in the first substrate.
[14] The light emitting rib according to [13], wherein the second substrate has a transparent electrode film on a surface facing the first substrate, and the convex portion is formed on the surface of the transparent electrode film. Liquid crystal cell.
[15] The liquid crystal cell according to any one of [10] to [14], which is a VA mode liquid crystal cell.
[16] A liquid crystal display device having the liquid crystal cell according to any one of [10] to [15].

According to the present invention, it is possible to easily and stably produce a liquid crystal cell substrate having an alignment control structure and an optical compensation capability. As a result, the viewing angle characteristics of the liquid crystal display device and reliability such as light leakage can be improved with almost no change in the manufacturing cost of the liquid crystal display device.
In addition, the alignment control structure according to the present invention can be effectively used particularly for control of vertical alignment because the depth of the alignment control structure can be increased. Furthermore, according to the present invention, for example, an orientation control structure including a complicated groove structure that is difficult to form by the method described in Patent Document 2 can be easily formed.

BEST MODE FOR CARRYING OUT THE INVENTION

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

  In this specification, the Re retardation value is calculated based on the following. Re (λ) represents in-plane retardation and retardation in the thickness direction at the wavelength λ. Re (λ) is measured by injecting light of wavelength λ nm in the normal direction by the parallel Nicols method. In the present specification, λ refers to 611 ± 5 nm, 545 ± 5 nm, 435 ± 5 nm for R, G, and B, respectively, and refers to 545 ± 5 nm or 590 ± 5 nm unless otherwise specified.

  In this specification, “substantially” for the angle means that the error from the exact angle is within a range of less than ± 5 °. Furthermore, the error from the exact angle is preferably less than 4 °, more preferably less than 3 °. With regard to retardation, “substantially” means that the retardation is within ± 5%. Furthermore, Re is not substantially 0 means that Re is 5 nm or more. In addition, the measurement wavelength of the refractive index indicates an arbitrary wavelength in the visible light region unless otherwise specified. In the present specification, “visible light” refers to light having a wavelength of 400 to 700 nm.

The present invention will be described in detail below.
[Method for manufacturing substrate for liquid crystal cell]
First, the manufacturing method of the liquid crystal cell substrate of the present invention will be described. An example of a method for producing a liquid crystal cell substrate of the present invention will be described with reference to FIG.
First, a transparent substrate 10 is prepared (FIG. 1 (a)). As the transparent substrate, a known glass plate such as a glass plate, low expansion glass, non-alkali glass, quartz glass plate, and a plastic film can be used. As a film thickness of a transparent substrate, 700-1200 micrometers is generally preferable. The transparent substrate 10 may have a black matrix 12 and a color filter 14 on the surface. The color filter 14 may be a color filter composed of R, G, B, or a color filter composed of R, G, B, W (white). Generally, these can be produced using a transfer material. The transparent substrate 10 may have an insulating film such as silicon oxide or silicon nitride on the surface.

  Next, the optically anisotropic layer 20 is formed on the surface of the transparent substrate 10 using the transfer material 16 having the optically anisotropic layer 20 on the surface of the transparent substrate 10. For example, the transfer material 16 has an adhesive layer 18 and an optically anisotropic layer 20 on the temporary support, and the adhesive layer 18 has a function of fixing the optical anisotropy 20 on the surface of the transparent substrate 10. It may be. The transfer material 16 having such an aspect is disposed with the surface of the adhesive layer 18 being the surface of the transparent substrate 10 and the temporary support (not shown in the drawing) is peeled off, whereby the optically anisotropic layer 20 is removed from the transparent substrate 10. It can be transferred to the surface (FIG. 1 (b)). For example, the transfer material can be attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the surface of the adhesive layer 18 facing the transparent substrate. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. Thereafter, the temporary support may be peeled off.

  There may be another layer transferred from the transfer material on the optically anisotropic layer 20, but since it is necessary to prevent impurities from entering the liquid crystal cell as much as possible, the optically anisotropic layer 20 In the case where there is another layer transferred from the transfer material on the surface, it is preferably removed, for example, during a process such as development of the transfer material or a cleaning process.

  Next, a groove-like missing portion 22 is provided in the transferred optically anisotropic layer 20 (FIG. 1C). As a method for forming a missing portion in the optically anisotropic layer 20, for example, the adhesive layer 18 is formed from a photosensitive resin composition and exposed through a mask having a predetermined pattern or exposed in a pattern by laser irradiation or the like. (In this specification, both patterns are referred to as “pattern exposure”), and the difference in solubility in the developer between the exposed part and the unexposed part is caused. While removing to make the adhesive layer 18 ′, a part of the optically anisotropic layer 20 is also removed simultaneously to form the optically anisotropic layer 20 ′. When the temporary support of the transfer material is made of a transparent film or the like, the adhesive layer 18 is placed on the surface of the transparent substrate, and before the temporary support is peeled off, a groove-like missing portion is formed by pattern exposure and development. In such a case, the missing portion 22 is formed simultaneously with the transfer of the optically anisotropic layer 20. The optically anisotropic layer 20 ′ provides the transparent substrate 21 with an optical compensation capability for the liquid crystal layer, and the groove-shaped missing portion 22 provides an alignment control capability for the liquid crystal layer. As described above, when the transfer material is used, the alignment control groove and the optically anisotropic layer can be simultaneously formed by one transfer-exposure-development process.

As described above, the pattern exposure may be performed by placing a predetermined mask above the optically anisotropic layer 20 and then exposing from above the mask through the mask, or without using a laser or an electron beam. The exposure may be performed while focusing on a predetermined position. Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 10-5000 mJ / cm < ² > normally, Preferably it is about 20-1000 mJ / cm < ² >.

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

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

  In order for the groove-shaped missing portion 22 to contribute to alignment control as an alignment control groove, the depth is preferably 0.2 to 5.0 μm, and preferably 0.5 to 3.5 μm. More preferred. For example, if a transfer material having an adhesive layer and an optically anisotropic layer is used as the transfer material, the depth of the groove-like missing portion can be easily adjusted to the preferred range by adjusting the thickness of these layers. it can. Further, by using a transfer material having a layer made of a photosensitive resin material as an adhesive layer, the shape, position, etc. of the missing portion can be easily controlled by pattern exposure and development. It is preferable that the side surface constituting the groove-like missing portion is inclined at a predetermined angle because the transparent conductive film covering this portion has good coverage. The direction of the inclination is preferably inclined so that the width of the missing portion becomes smaller in the depth direction of the groove. It is preferable to incline from 0 to 40 ° with respect to the vertical plane, and more preferably from 5 to 30 °. The side surface of the groove can be inclined at a predetermined angle by a method such as post baking. The shape of the orientation control groove is not particularly limited, and may be a stripe-like groove formed in parallel with one direction or a groove formed in a lattice shape. It is preferable that the groove has a shape having a portion intersecting at least in two directions, preferably 90 degrees, or a shape having an “L-shaped” portion bent by 90 degrees (for example, the shape shown in FIG. 6). .

Furthermore, a transparent electrode film 24 that can provide an electric field to the liquid crystal layer may be formed on the surface of the optically anisotropic layer 20 ′ (FIG. 1D). However, it is preferable to adjust the thicknesses of the pressure-sensitive adhesive layer, the optically anisotropic layer, and the transparent electrode film so that the depth of the missing portion 22 ′ is within the above range even after the transparent electrode film 24 is formed.
Furthermore, after forming the transparent electrode film 24, a step of forming an alignment film for controlling the alignment of liquid crystalline molecules in the liquid crystal layer may be performed.

[Liquid Crystal Cell and Manufacturing Method]
The substrate for a liquid crystal cell produced by the above method is usually used for one of a pair of substrates constituting a liquid crystal display device. For example, the liquid crystal cell substrate (hereinafter referred to as “first substrate”) produced as described above is another substrate (hereinafter referred to as “second substrate”) with the surface where the groove-like missing portion is formed inside. The liquid crystal cell can be manufactured by injecting liquid crystal between the first and second substrates arranged opposite to each other to form a liquid crystal layer. In the present invention, in order to further enhance the alignment control ability of the alignment control groove (groove-shaped missing portion) formed in the first substrate, the second substrate is formed on the opposite surface of the first substrate. It is preferable to use a substrate having a concave portion or a convex portion at a position corresponding to the position of the orientation control groove.

  In FIG. 2, the cross-sectional schematic diagram of an example of the liquid crystal cell of this invention is shown. 2, the same members as those shown in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted. The liquid crystal cell shown in FIG. 2 has a first substrate 10A and a second substrate 10B manufactured by the above method, and has a liquid crystal layer containing liquid crystal molecules 32 sandwiched between them. The substrate 10A may have a black matrix and a color filter between the optically anisotropic layer 20 'and the transparent substrate 10. The first substrate 10A is arranged with the surface provided with the alignment control groove 22 'facing the liquid crystal layer. Transparent electrode films 24 and 26 are formed on the opposing surfaces of the first substrate 10A and the second substrate 10B, respectively, so that an electric field can be applied to the liquid crystalline molecules 32 in the liquid crystal layer. . In the transparent electrode film 26 of the second substrate 10B, a slit 28 is formed at a position corresponding to the alignment control groove 22 ′, which contributes to controlling the alignment of the liquid crystal molecules 32 in the liquid crystal layer. Yes. The slit 28 can be formed by, for example, etching using a photoresist.

  With respect to the liquid crystal cell of FIG. 2, the operation of the alignment control groove 22 'and the slit 28 will be described. When a voltage is applied to the transparent electrode film 24 of the substrate 10A and the transparent electrode film 26 of the substrate 10B, an electric field distribution is formed between the substrates in which the electric field is uniformly changed in a direction perpendicular to the substrate surface. In the locations where the alignment control grooves 22 ′ and the slits 28 are present, a non-uniform electric field distribution is formed in which the electric field strength changes in the direction indicated by the arrows in the figure, not perpendicular to the substrate surface. The liquid crystal molecules 32 existing in and in the vicinity of the alignment control groove 22 ′ and the slit 28 are inclined in different directions as shown in FIG. 2 by the action of this non-uniform electric field. This alignment state also affects the alignment state of liquid crystal molecules present in a uniform electric field, and these molecules are similarly tilted. By the above action, the alignment control groove 22 ′ and the slit 28 control the alignment of the liquid crystal molecules in the liquid crystal layer.

  In FIG. 3, the cross-sectional schematic diagram of the other example of the liquid crystal cell of this invention is shown. In FIG. 3, the same members as those shown in FIGS. 1 and 2 are denoted by the same reference numerals, and detailed description thereof is omitted. The liquid crystal cell shown in FIG. 3 has a first substrate 10A and a second substrate 10B 'manufactured by the above method, and has a liquid crystal layer containing liquid crystal molecules 32 sandwiched between them. On the surface of the transparent electrode film 26 of the second substrate 10B ′, light-shielding ribs 30 are formed at positions corresponding to the alignment control grooves 22 ′ of the first substrate 10A, and the liquid crystalline molecules in the liquid crystal layer It contributes to controlling the orientation of 32. The light-shielding rib 30 can be manufactured by a method using a pattern exposure and a development process using a photosensitive organic insulating material having a dielectric constant lower than that of a liquid crystal material, for example.

  The operation of the alignment control groove 22 ′ and the light shielding rib 30 in the liquid crystal cell of FIG. 3 is the same as described above. The intensity of the electric field changes in the direction indicated by the arrow in the drawing by the alignment control groove 22 ′ and the light shielding rib 30. A non-uniform electric field distribution is formed, whereby the liquid crystal molecules 32 existing in or near the alignment control groove 22 ′ and in the vicinity of the light shielding rib 30 are inclined in different directions as shown in FIG. To do. This alignment state also affects the alignment state of liquid crystal molecules present in a uniform electric field, and these molecules are similarly tilted.

  Note that there is no particular limitation on the shape, depth, height, or the like of the concave portion or the convex portion formed on the second substrate as long as it can contribute to orientation control by the above action. Generally, it is preferable that the depth of the concave portion such as a slit is 0.2 to 5.0 μm. Moreover, it is preferable that the convex part which is a light shielding rib etc. generally has a height of 0.5 to 2.0 μm.

[Liquid Crystal Display]
FIG. 4 is a schematic cross-sectional view of an example of the liquid crystal display device of the present invention. 4, the same members as those shown in FIGS. 1 to 3 are denoted by the same reference numerals, and detailed description thereof is omitted. The liquid crystal display device shown in FIG. 4 has the liquid crystal cell shown in FIG. 2, and is an example in which the first substrate 10A is a color filter substrate and the second substrate 10B is a TFT array substrate. On both sides of the liquid crystal cell, polarizing plates made of a polarizing layer 33 sandwiched between protective films 34 and 35 made of cellulose acetate (TAC) film or the like are arranged. The protective film 35 on the liquid crystal cell side may be optically anisotropic, and in such a case, it contributes to optical compensation of the liquid crystal cell. The display mode is not particularly limited, and can be used for all transmissive and reflective liquid crystal display devices. In particular, the present invention is effective for the VA mode where color viewing angle characteristics are desired to be improved.

  Hereinafter, materials and the like used in the method for producing a liquid crystal cell substrate of the present invention will be described in detail. In particular, the transfer material used in the production method of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below, and other embodiments can be produced with reference to the following description and conventionally known methods.

[Transfer material]
In the method for producing a substrate for a liquid crystal cell of the present invention, a transfer material is used. The transfer material is preferably a transfer material having a temporary support, at least one optically anisotropic layer, and at least one adhesive layer. When transferred to the transparent substrate, the temporary support is removed, and the optically anisotropic layer and the adhesive layer are transferred onto the transparent substrate. FIG. 5 is a schematic cross-sectional view of some examples of transfer materials that can be used in the present invention. The transfer material shown in FIG. 5A has an optically anisotropic layer 52 and an adhesive layer 54 on a transparent or opaque temporary support 50. This transfer material may have other layers. For example, as shown in FIG. 5B, unevenness on the counterpart substrate side may be formed between the support 50 and the optically anisotropic layer 52 during transfer. It may have a layer 56 for controlling mechanical properties such as cushioning for absorbing or imparting unevenness follow-up, and, as shown in FIG. At the time of production, a layer 58 that functions as an alignment layer for controlling the alignment of the liquid crystalline molecules in the optically anisotropic layer 52 may be disposed. Moreover, as shown in FIG.5 (d), you may provide the protective layer 60 which can peel on the outermost surface for the objectives, such as surface protection of the photosensitive resin layer 54. FIG.

[Temporary support]
The temporary support used for the transfer material may be transparent or opaque and is not particularly limited. Examples of the polymer constituting the support include cellulose ester (eg, cellulose acetate, cellulose propionate, cellulose butyrate), polyolefin (eg, norbornene polymer), poly (meth) acrylic acid ester (eg, polymethyl). Methacrylate), polycarbonate, polyester and polysulfone, and norbornene-based polymers. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and from the viewpoint of low birefringence, cellulose ester and norbornene are preferred. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. Inexpensive polycarbonate, polyethylene terephthalate and the like are also preferably used.

[Optically anisotropic layer]
The optically anisotropic layer in the transfer material is not particularly limited as long as it has at least one incident direction in which Re is not substantially zero when the anisotropy is measured, that is, has optical characteristics that are not isotropic. However, it is preferably formed from a composition containing at least one liquid crystalline compound, and contains at least one liquid crystalline compound, from the viewpoint of easy control of optical properties used in the liquid crystal cell. A layer formed by curing the liquid crystal layer by irradiating it with ultraviolet rays is desirable.

[Optically Anisotropic Layer Consisting of Composition Containing Liquid Crystalline Compound]
As described above, the optically anisotropic layer functions as an optically anisotropic layer that compensates the viewing angle of the liquid crystal display device by being incorporated in the liquid crystal cell. Optically required for optical compensation in combination with other layers (for example, an optically anisotropic layer disposed outside the liquid crystal cell) as well as an aspect in which the optically anisotropic layer alone has sufficient optical compensation capability There may also be an embodiment that satisfies the characteristics. In addition, the optically anisotropic layer of the transfer material does not need to satisfy the optical characteristics sufficient for the optical compensation capability. The characteristic may be expressed or changed, and finally the optical characteristic necessary for optical compensation may be exhibited.

  As described above, the optically anisotropic layer is preferably formed from a composition containing at least one liquid crystalline compound. In general, liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type based on their shapes. In addition, there are low and high molecular types, respectively. Polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). In this embodiment, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a disk-like liquid crystal compound is preferably used. Two or more kinds of rod-like liquid crystalline compounds, two or more kinds of disc-like liquid crystalline compounds, or a mixture of a rod-like liquid crystalline compound and a disk-like liquid crystalline compound may be used. Since the change in temperature and humidity can be reduced, it is more preferable to use a rod-like liquid crystal compound or a disk-like liquid crystal compound having a reactive group. In the case of a mixture, at least one of the reactive groups in one liquid crystal molecule is formed. Is more preferably 2 or more. The liquid crystalline compound may be a mixture of two or more, and in that case, at least one preferably has two or more reactive groups. The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, and more preferably 0.5 to 10 μm.

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

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

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

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

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

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

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

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

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

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

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

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

  Preferred examples of the discotic compound are shown below.

  The optically anisotropic layer is formed by applying a composition containing a liquid crystal compound (for example, a coating solution) to the surface of an alignment layer described later to obtain an alignment state exhibiting a desired liquid crystal phase, and then heating the alignment state. Or it is preferable that it is the layer produced by fixing by irradiation of ionizing radiation. It is preferable that the optically anisotropic layer exhibits biaxiality because a liquid crystal cell, particularly a VA mode liquid crystal cell, can be optically compensated accurately. When a rod-like liquid crystal compound having a reactive group is used as the liquid crystal compound, polarized light is applied to the cholesteric alignment or the twisted hybrid cholesteric alignment while the inclination angle gradually changes in the thickness direction in order to develop biaxiality. It is necessary to distort by. As a method for distorting the alignment by irradiation with polarized light, a method using a dichroic liquid crystalline polymerization initiator (EP1389199 A1) or a method using a rod-like liquid crystalline compound having a photoalignable functional group such as a cinnamoyl group in the molecule (special feature). No. 2002-6138). Any of them can be used in the present invention.

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

  When a discotic liquid crystalline compound having a reactive group is used as the liquid crystalline compound, it may be fixed in any alignment state of horizontal alignment, vertical alignment, tilt alignment, and twist alignment, but horizontal alignment, vertical alignment Twist orientation is preferred and horizontal orientation is most preferred. In the present specification, “horizontal alignment” means that in the case of a rod-like liquid crystal, the molecular long axis and the horizontal plane of the support are parallel, and in the case of a disc-like liquid crystal, the disc surface of the core of the disc-like liquid crystal compound. And the horizontal plane of the transparent support is parallel, but it is not required to be strictly parallel, and in this specification, an inclination angle with the horizontal plane is less than 10 degrees. To do. In the present specification, when referred to as “horizontal orientation”, the inclination angle is preferably 0 to 5 degrees, more preferably 0 to 3 degrees, further preferably 0 to 2 degrees, and most preferably 0 to 1 degree.

  When two or more optically anisotropic layers formed from a composition containing a liquid crystalline compound are laminated, the combination of the liquid crystalline compounds is not particularly limited, and a laminate of layers made of a discotic liquid crystalline compound, It may be a laminate of layers made of a rod-like liquid crystalline compound, or a laminate of layers made of a disk-like liquid crystalline compound and a layer made of a rod-like liquid crystalline compound. The combination of the alignment states of the layers is not particularly limited, and optically anisotropic layers having the same alignment state may be stacked, or optically anisotropic layers having different alignment states may be stacked.

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

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

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

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

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

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

By containing at least one compound represented by the following general formulas (1) to (3) in the composition for forming the optically anisotropic layer, the molecules of the liquid crystalline compound are substantially horizontally aligned. be able to.
Hereinafter, the following general formulas (1) to (3) will be described in order.

General formula (1)

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

General formula (2)

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

General formula (3)

In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a substituent. The substituents represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably the substituents represented by R ¹ , R ² and R ³ in the general formula (I). It is listed as a thing. As the horizontal alignment agent used in the present invention, the compounds described in JP-A-2005-099248 can be used, and the synthesis method of these compounds is also described in the specification.

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

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

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

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

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

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

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

  The optically anisotropic layer can be transferred by aligning the liquid crystalline compound on the temporary alignment layer, fixing the alignment, and then using an adhesive on the transparent support, but from the viewpoint of productivity. Is preferably formed directly without transfer.

[Adhesive layer]
The adhesive layer used for the transfer material is preferably a photosensitive resin layer made of a photosensitive resin composition. The photosensitive resin layer is positive or negative if a difference in transferability to the substrate (for example, a difference in solubility in a developing solution) occurs between the exposed and unexposed areas when light is irradiated through a mask or the like. There is no particular limitation as it may be a mold. The photosensitive resin layer is formed from a photosensitive resin composition including at least (1) an alkali-soluble resin, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or a photopolymerization initiator system. Is preferred.
Hereinafter, the components (1) to (3) will be described.

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

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

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

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used for the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is disclosed. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B 51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 Trihalomethyl described in Saisho - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the colored resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

  In addition, when providing a color filter layer on a liquid crystal cell substrate in the production method of the present invention, a transfer material is prepared using a photosensitive resin layer further containing the following colorant instead of the adhesive layer, The color filter layer may be provided by using it in accordance with the method using the transfer material described above or below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Moreover, the following commercially available surfactant can also be used as it is. Examples of commercially available surfactants that can be used include F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) or other fluorine-based surfactants or silicon-based surfactants Can be mentioned. Polysiloxane polymers KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) can also be used as the silicon surfactant.

[Other layers]
Between the temporary support and the optically anisotropic layer in the transfer material, a thermoplastic resin layer for controlling the mechanical properties and the unevenness followability of the transfer material may be provided. As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxy Chill nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

  In the transfer material, an intermediate layer may be provided for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity. The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

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

  A thin protective film is preferably provided on the resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the resin layer. As the protective film material, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.

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

As an example of the transfer material used in the method for manufacturing a substrate for a liquid crystal cell of the present invention and the method for manufacturing a liquid crystal cell,
(1) a transfer material having at least one optically anisotropic layer and at least one photosensitive resin layer on a temporary support;
(2) A transfer material having at least one optically anisotropic layer and at least one photosensitive resin layer on a temporary support, wherein the optically anisotropic layer has a reactive group. A transfer material formed from a composition comprising a composition containing a polymerization initiator having a photosensitive resin layer having two or more different photoreaction mechanisms;
(3) The optically anisotropic layer is a layer formed by applying and drying a solution containing a liquid crystalline compound having at least one reactive group to form a liquid crystal phase, and then fixing by irradiation with heat or ionizing radiation ( 1) or (2) transfer material;
(4) The transfer material according to (2) or (3), wherein the reactive group is an ethylenically unsaturated group;
(5) The transfer material according to any one of (1) to (4), wherein the optically anisotropic layer is formed from a composition containing a radical polymerization initiator;
(6) The said photosensitive resin layer is formed from the composition containing the polymerization initiator which has a 2 or more types of different photoreaction mechanism, and at least 1 type is a radical polymerization initiator of (1)-(5) Transfer material;
(7) The photosensitive resin layer is formed from a composition containing a polymerization initiator having two or more different photoreaction mechanisms, and at least one of them is a cationic polymerization initiator (1) to (6) Any transfer material;
(8) The transfer material according to any one of (1) to (7), wherein the optically anisotropic layer or the photosensitive resin layer contains a compound having at least one epoxy group;
(9) Any of (1) to (8), wherein the optically anisotropic layer or the photosensitive resin layer contains a compound having at least one selected from a carboxyl group, a hydroxyl group, an amino group, and a thiol group. A liquid crystal cell and a production method thereof.
(10) The transfer material according to any one of (1) to (9), wherein the optically anisotropic layer is formed directly on the temporary support or directly on a rubbing alignment layer formed on the support. ;
(11) The transfer material according to any one of (1) to (10), wherein the liquid crystalline compound is a rod-like liquid crystal;
(12) The transfer material according to any one of (1) to (11), wherein the liquid crystal phase of the composition is a cholesteric phase;
(13) The optical properties of the optically anisotropic layer are such that the front retardation (Re) is not 0, and the in-plane slow axis is the tilt axis (rotation axis) and +40 with respect to the normal direction of the optical compensation sheet A retardation value measured by making light having a wavelength λ nm incident from a tilted direction, and a direction tilted by −40 ° with respect to the normal direction of the optical compensation sheet with the in-plane slow axis as the tilt axis (rotation axis) The transfer material according to any one of (1) to (12), wherein the retardation value measured by making light having a wavelength of λ nm incident is substantially equal; and (14) The front surface of the optically anisotropic layer Retardation (Re) is 20 to 200 nm, and light having a wavelength of λ nm is incident from a direction inclined + 40 ° with respect to the normal direction of the optically anisotropic layer with the in-plane slow axis as the tilt axis (rotation axis). The retardation value measured by One of the transfer material of a 250nm (1) ~ (13); and the like.

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

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

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

(Preparation of coating liquid LC-1 for optically anisotropic layer)
After the following composition was prepared, it was filtered through a polypropylene filter having a pore size of 0.2 μm and used as a coating liquid LC-1 for an optically anisotropic layer.
LC-1-1 was obtained from Tetrahedron Lett. Synthesized according to the method described in Journal, Vol. 43, page 6793 (2002). LC-1-2 was synthesized by the method described in EP1388538A1, page 21.
──────────────────────────────────――
Coating composition for optically anisotropic layer (%)
──────────────────────────────────――
Bar-shaped liquid crystal (Paliocolor LC242, BASF Japan) 22.0
Chiral agent (Paliocolor LC756, BASF Japan) 3.40
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COO-Ph-COOH 3.30
CH ₂ = CH-COO (CH ₂ ) ₄ COO-Ph-COOH 3.30
(However, Ph represents a phenylene group)
4,4′-Azoxydianisole 0.52
Horizontal alignment agent (LC-1-1) 0.10
Photopolymerization initiator (LC-1-2) 1.36
Methyl ethyl ketone 66.2
──────────────────────────────────――

  Below, the manufacturing method of the coating liquid for photosensitive resin layers is demonstrated. Table 1 shows the composition of each coating solution for the photosensitive resin layer.

The compositions in Table 1 are as follows.
[K pigment dispersion composition]
──────────────────────────────────――
K pigment dispersion composition (%)
──────────────────────────────────――
Carbon black (Degussa, Special Black 250)
13.1
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo]
-Butyroylaminobenzimidazolone
0.65
Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio (weight average molecular weight 37,000) 6.72
Propylene glycol monomethyl ether acetate 79.53
──────────────────────────────────――

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

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

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

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

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

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

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

(Preparation of coating solution PP-K1 for light-shielding barrier layer)
The coating solution PP-K1 for the light-shielding barrier layer is first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3 in the amounts shown in Table 1 -Bromophenyl] -s-triazine and Megafac F-176PF Surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. It was obtained by

(Preparation of coating solution PP-R1 for photosensitive resin layer)
The coating liquid PP-R1 for the photosensitive resin layer was first weighed in the amounts of R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, at a temperature of 24 ° C. (± 2 ° C.). Mix and stir at 150 rpm for 10 minutes, then methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole in the amounts listed in Table 1 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethyl) -3-bromophenyl] -s-triazine and phenothiazine were weighed, and the temperature was 24 ° C. (± 2 ° C.). And then stirred at 150 rpm for 10 minutes, and then weighed out the amount of ED152 shown in Table 1 and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir for a minute, and then weigh out the Megafac F-176PF surfactant 1 in the amount shown in Table 31, add it at a temperature of 24 ° C. (± 2 ° C.), stir at 30 rpm for 30 minutes, and filter through nylon mesh # 200. It was obtained by

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

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

(Preparation of coating liquid PP-X1 for adhesive layer)
The coating solution PP-X1 for the photosensitive resin layer includes propylene glycol monomethyl ether acetate and methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4 as shown in Table 1. -Weigh out oxadiazole and phenothiazine, add in this order at a temperature of 25 ° C (± 2 ° C), stir at a temperature of 40 ° C (± 2 ° C) for 150 minutes, and then add the amount of megafac shown in Table 1 F-176PF surfactant 1 was weighed out, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through nylon mesh # 200.

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

(Preparation of transfer material for optically anisotropic layer)
A thermoplastic resin layer coating solution CU-1 was applied and dried on a 75 μm thick polyethylene terephthalate film temporary support using a slit nozzle. Next, the coating liquid AL-1 was applied and dried. The film thickness of the thermoplastic resin layer was 14.6 μm, and the alignment layer was 1.6 μm. Subsequently, after rubbing the formed alignment layer, the coating liquid LC-1 for optically anisotropic layer is applied thereon with a # 6 wire bar coater, and the film surface temperature is 95 ° C. for 2 minutes by heating and aging. And a layer having a uniform liquid crystal phase was formed. Further, immediately after aging, this layer was irradiated with polarized UV in a nitrogen atmosphere with an oxygen concentration of 0.3% or less using POLUV-1 so that the transmission axis of the polarizing plate was in the TD direction of the temporary support. (An illuminance of 200 mW / cm ² and an irradiation amount of 200 mJ / cm ² ) was used to immobilize the optical anisotropic layer to form an optically anisotropic layer having a thickness of 2.8 μm. Finally, the photosensitive resin composition PP-X1 was applied and dried to prepare a photosensitive resin transfer material X-1 for an optically anisotropic layer, which is Example 1 of the present invention.

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

(Production of photosensitive resin transfer material for RGB)
On the roll-shaped polyethylene terephthalate film temporary support body of thickness 75micrometer, the coating liquid CU-1 for thermoplastic resin layers was apply | coated and dried using the slit-shaped nozzle. Next, the alignment layer coating liquid AL-1 was applied and dried. The film thickness of the thermoplastic resin layer was 14.6 μm, and the alignment layer was 1.6 μm. Subsequently, the photosensitive resin composition PP-R1 was applied and dried to prepare an R photosensitive resin transfer material R-1.
For G and B, PP-G1 and PP-B1 were used instead of PP-R1, and photosensitive resin transfer materials G-1 and B-1 for G and B were produced.

(Phase difference measurement)
By the parallel Nicol method using a fiber-type spectrometer, the front retardation Re (0) at the wavelength λ and the retardations Re (40), Re (−) when the sample is tilted ± 40 degrees around the slow axis as the rotation axis. 40) was measured. Table 3 shows the phase difference measurement results of the optically anisotropic layer of Example 1.

(Production of color filter)
-Formation of black (K) image-
The alkali-free glass substrate to be the support is washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after pure water shower washing, a silane coupling solution (N-β (Aminoethyl) γ-aminopropyltrimethoxysilane 0.3% aqueous solution, trade name: KBM603, Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.
After peeling off the protective film of the photosensitive resin transfer material K-1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries (Lamic II type)), a rubber roller temperature of 130 ° C. Lamination was performed at a linear pressure of 100 N / cm and a conveying speed of 2.2 m / min.
After peeling the temporary support, the exposure mask with the substrate and mask (quartz exposure mask with image pattern) standing upright with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp. The distance between the surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 70 mJ / cm ² .
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Subsequently, a sodium carbonate developer (0.06 mol / L sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T- CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterned pixel.
Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) with a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a shower and a rotating brush having nylon bristles to obtain an image of black (K), and then further from the side of the resin layer to the substrate with an ultrahigh pressure mercury lamp at a light of 500 mJ / cm ² . After post exposure, heat treatment was performed at 220 ° C. for 15 minutes.
The substrate on which the K image was formed was washed again with a brush as described above, and after pure water shower washing, the substrate was heated at 100 ° C. for 2 minutes without using a silane coupling solution.

-RGB pixel formation-
After peeling off the protective film of the photosensitive resin transfer material R-1, the black (K) image was formed using a laminator (manufactured by Hitachi Industries (Lamic II type)) and heated at 100 ° C. for 2 minutes. The laminated substrate was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After peeling off the temporary support, the distance between the exposure mask surface and the photosensitive resin layer is set to 40 μm and the exposure dose is set to 50 mJ with a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp. / Cm < ² >.
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the 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 Photo Film Co., Ltd.) and 2-propanol mixed solution (mixing ratio 4: 1), shower developing with cone type nozzle pressure of 0.15 MPa, removing surface development residue with a rotating brush. Thus, a patterning pixel was obtained.
Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) at a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a shower and a rotating brush having nylon bristles, 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) pixels-
Using the photosensitive resin transfer material G-1, a green (G) pixel was obtained on the substrate on which the red (R) pixel was formed in the same process as the photosensitive resin transfer material R-1.

-Formation of blue (B) pixels-
Using the photosensitive resin transfer material B-1, a blue (B) pixel was obtained by the same process on the substrate on which the red (R) pixel and the green (G) pixel were formed.

  The substrate on which the black image and the R, G, and B pixels are formed is again cleaned with a brush as described above. After pure water shower cleaning, the substrate is heated at 100 ° C. for 2 minutes to obtain a target color filter. Produced.

(Preparation of optically anisotropic layer having orientation control groove)
After the protective film of the photosensitive resin transfer material PP-X1 is peeled off, a laminator (manufactured by Hitachi Industries (Lamic II type)) is used to form the black (K) image and then heated at 100 ° C. for 2 minutes. The laminated substrate was laminated at a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 1.4 m / min.
After peeling off the temporary support, the 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 >.
Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoamer-containing, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the 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 Photo Film Co., Ltd.) and 2-propanol mixed solution (mixing ratio 4: 1), shower developing with cone type nozzle pressure of 0.15 MPa, removing surface development residue with a rotating brush. It was. In this step, the optically anisotropic layer and the photosensitive resin layer were developed and a part thereof was removed 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, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1” (manufactured by Fuji Photo Film Co., Ltd.)) at a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a shower and a rotating brush having nylon bristles, 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.
In this manner, a liquid crystal cell substrate was produced. The prepared substrate is formed on the surface with a color filter (black image and RGB image) and a pattern having an “L-shaped” portion shown in FIG. 6 on the color filter. The laminate had a photosensitive resin layer provided with a control groove 22 and an optically anisotropic layer. The depth of the orientation control groove 22 was 2.4 μm.

(Formation of transparent electrode)
On the optically anisotropic layer of the liquid crystal cell substrate produced above, a transparent electrode film was formed by sputtering of ITO. Even after the transparent electrode film was formed, the depth of the orientation control groove was the same as that before the transparent electrode film was formed, and was 2.4 μm.

(Formation of alignment layer)
Furthermore, an alignment layer was provided on the transparent electrode. 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.

(Preparation of opposite substrate)
An ITO transparent electrode film was formed on the alkali-free glass by sputtering. Specifically, after evacuation to about 10 ⁻⁵ Pa in a vacuum chamber, the substrate is heated to 240 degrees with a heater, plasma discharge is performed in an argon gas atmosphere of 10 ⁻¹ Pa, and the target surface is exposed to ITO. And was deposited to a thickness of 1000A. Next, a slit pattern was formed in the formed ITO transparent electrode film by the following method. First, a photoresist for TFT (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was uniformly coated on the surface of the ITO transparent electrode film by spin coating to a thickness of 2 μm. After pre-baking in a 100 ° C. baking oven, a pattern was baked using a photomask having a desired pattern using an exposure apparatus (Nikon stepper). The exposure amount and the exposure time were determined by appropriately selecting the optimum equipment conditions. The exposed substrate was developed with a developer (containing tetramethylammonium hydroxide: manufactured by Tokyo Ohka Kogyo Co., Ltd.) and post-baked in a baking oven at 120 ° C. to remove the residual solvent and fix the shape. Next, perform etching while spraying the ITO etchant (containing ferric chloride: manufactured by Kanto Chemical Co., Ltd.) with a swinging shower head, and confirm that the ITO film has completely dissolved. Washed off and dried with a high-pressure air knife using dry air. Next, the resist was peeled off. While spraying a resist stripping solution (containing 2-aminoethanol and NMP: manufactured by Tokyo Ohka Kogyo Co., Ltd.) with a shower head, the resist was stripped by applying a roll brush. The stripping solution was swept away with a hot water shower and an air knife. In this way, a slit having a depth of 0.1 μm was formed in the ITO transparent electrode film. The slits were formed so as to correspond to the alignment control grooves of the liquid crystal cell substrate produced above.

(Formation of facing side alignment layer)
A polyimide alignment layer was formed on the ITO transparent electrode film provided with the slits. 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.
In this way, an ITO transparent electrode film having a slit pattern and an opposing substrate having an alignment layer were produced on a glass substrate.

(Seal pattern formation)
A seal pattern was 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.

(Overlapping)
The liquid crystal cell substrate produced above and the opposite substrate are overlapped at the correct position, that is, when both substrates are arranged opposite to each other, the alignment control grooves and the electrode film slits exist at the opposite positions. In this way, alignment was performed using an overlaying apparatus. In this state, while applying a pressure of 0.03 Mpa, both the bonded substrates were heat-treated at 180 ° C. for 90 minutes to cure the sealing agent to obtain a laminate of two substrates. A balloon-type baking apparatus was used for baking.

(Liquid crystal injection)
A liquid crystal material was injected into the substrate laminate using a liquid crystal injection device. The liquid crystal material is in Merck MLC-6608, which was placed in a liquid crystal dish, and degassed and held 60 minutes under a vacuum of 10 ^-1 Pa with a vacuum chamber together with the substrate stack. After sufficiently evacuating the vacuum, the portion of the inlet provided in the seal was immersed in the liquid crystal and then returned to atmospheric pressure and held for 180 minutes to fill the gap between the glass substrates with the liquid crystal. Thereafter, the substrate laminate was taken out from the injection apparatus, and a UV curable epoxy adhesive was applied to the injection port portion and cured to obtain a liquid crystal cell.

(Polarizing plate pasting)
A polarizing plate HLC2-2518 (manufactured by Sanritz Co., Ltd.) was attached to both sides of the liquid crystal cell in an arrangement in which the absorption axes were orthogonal to each other to obtain a liquid crystal panel.

(Production of VA-LCD of Example 1)
A cold cathode tube for a color liquid crystal display device was used as a backlight. A liquid crystal cell provided with the above polarizing plate was placed on the backlight, and VA-LCDs of Examples were produced.

(Production of Comparative Example VA-LCD)
Instead of forming the optically anisotropic layer in the liquid crystal cell, instead of forming the optically anisotropic layer on the protective film on the liquid crystal cell side of the lower polarizing plate, an optically anisotropic layer having a thickness of 2.75 μm was prepared. A VA-LCD of Comparative Example 1 was produced in the same manner as in Example except that the isotropic layer was formed.

(Comparison of light leakage of VA-LCD)
The produced liquid crystal display devices of the example and the comparative example were taken out after being put in a constant temperature layer at 60 ° C. and 95% in a driving state for 24 hours and left at 25 ° C. and 50% for 1 hour, and then light leakage on a black display screen Was visually observed. The results are shown in Table 3.

It is a schematic diagram which shows the flow of an example of the manufacturing method of the board | substrate for liquid crystal cells of this invention. It is a schematic sectional drawing of an example of the liquid crystal cell of this invention. It is a schematic sectional drawing of the other example of the liquid crystal cell of this invention. It is a schematic sectional drawing of an example of the liquid crystal display device of this invention. It is a schematic sectional drawing of the transfer material which can be used for the method of this invention. It is the upper surface schematic diagram of the board | substrate for liquid crystal cells produced in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Transparent substrate 10A 1st board | substrate 10B 2nd board | substrate 12 Black matrix 14 Color filter layer 16 Transfer material 18 Adhesive layer 20, 20 'Optical anisotropic layer 22, 22' Orientation control groove | channel 24, 26 Transparent electrode film 25, 27 Alignment layer 28 Slit 30 Light-shielding rib 31 TFT drive element 32 Liquid crystal molecule 33 Polarizing layer 34 Protective film 35 Protective film or optical compensation film

Claims (16)

A method for producing a substrate for a liquid crystal cell having an alignment control groove,
At the same time as or after forming the optically anisotropic layer transferred from the transfer material on the surface of the transparent substrate, a groove-like missing portion is provided in the optically anisotropic layer to form an alignment control groove. The manufacturing method of the board | substrate for liquid crystal cells containing these.   The method according to claim 1, wherein the depth of the groove-like missing portion is 0.2 to 5.0 μm.   The method according to claim 1, wherein the side surface constituting the groove-like missing portion is inclined at a predetermined angle.   The method according to claim 1, wherein the groove-like missing portion is formed by pattern exposure and development.   The method according to claim 4, wherein the transfer material has at least one optically anisotropic layer and at least one photosensitive resin layer on a temporary support.   The method according to claim 1, further comprising forming a transparent electrode film on the optically anisotropic layer. Preparing a first substrate obtained by the method according to any one of claims 1 to 6;
Placing the first substrate opposite the second substrate with the surface on which the orientation control groove is formed facing inside;
And a step of injecting liquid crystal between the first and second substrates arranged to face each other to form a liquid crystal layer.   The method according to claim 7, further comprising: forming a concave portion or a convex portion on a surface of the second substrate facing the first substrate at a position corresponding to the alignment control groove formed in the first substrate. The method described.   A liquid crystal cell substrate produced by the method according to claim 1.   10. A liquid crystal cell substrate according to claim 9, wherein the liquid crystal cell has first and second substrates and a liquid crystal layer sandwiched between the first and second substrates, wherein at least the first substrate is a liquid crystal cell. A liquid crystal cell in which the substrate is disposed with the surface on which the alignment control groove is formed facing the liquid crystal layer.   The liquid crystal cell according to claim 10, wherein the second substrate has a recess at a position corresponding to an alignment control groove provided in the first substrate, on a surface facing the first substrate.   The liquid crystal cell according to claim 11, wherein the second substrate has a transparent electrode film on a surface facing the first substrate, and the concave portion is a slit formed in the transparent electrode film.   The liquid crystal cell according to claim 10, wherein the second substrate has a convex portion on a surface facing the first substrate at a position corresponding to an alignment control groove formed in the first substrate.   The liquid crystal according to claim 13, wherein the second substrate has a transparent electrode film on a surface facing the first substrate, and the convex portion is a light shielding rib formed on the surface of the transparent electrode film. cell.   The liquid crystal cell according to claim 10, which is a VA mode liquid crystal cell. The liquid crystal display device which has a liquid crystal cell of any one of Claims 10-15.

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