JP4739066B2 - Projection for liquid crystal alignment control, and composition, resin transfer material, method for manufacturing liquid crystal alignment control projection, substrate for liquid crystal display device, liquid crystal display element, and liquid crystal display device - Google Patents

Description

  The present invention relates to a liquid crystal alignment control protrusion, a composition and a resin transfer material for forming the protrusion, a method of manufacturing a liquid crystal alignment control protrusion using the composition and the resin transfer material, and the liquid crystal alignment control protrusion The present invention relates to a substrate for a liquid crystal display device, a liquid crystal display element using the same, and a liquid crystal display device.

  In recent years, a liquid crystal display (LCD) has been most widely used as a flat panel display to replace a CRT (Cathode-Ray Tube) display, and its expectation is also great. In particular, thin film transistor (TFT) type LCDs (TFT-LCDs) are expected to further expand the market by application to personal computers, word processors, office automation equipment, portable televisions, etc. There is a need for further improvements in quality.

  Currently, the most widely used method among TFT-LCDs is a normally white mode TN (Twisted Nematic) type LCD. However, the TN type LCD has a drawback that the viewing angle is narrow, and the display state differs depending on the position where the display screen is observed. For this reason, the TN type LCD has a problem that its application is limited. The problem with TN-type LCDs is that they can be displayed by holding a liquid crystal between a pair of substrates with electrodes and applying a voltage between the electrodes (for example, a simple matrix type or a plasma addressed type LCD). This is also a problem that occurs in the same way.

  That is, such an LCD can be seen almost white in any orientation in a white display state where no voltage is applied. However, in the black display state in which a predetermined voltage is applied, the obliquely incident light passes obliquely with respect to the liquid crystal molecules aligned in the vertical direction. Therefore, when the black display LCD is observed obliquely, the deflection direction Will be twisted to some extent, and will appear halftone (gray) rather than completely black.

  Further, in the halftone display state in which the intermediate voltage is applied, the liquid crystal display rises halfway in the middle portion of the cell, and is displayed in halftone (gray) for vertically incident light. However, in the halftone display state, the appearance of light incident obliquely on the left and right differs depending on the incident direction. Specifically, as described in FIG. 2 (2) of Patent Document 1 below, the liquid crystal molecules are aligned in parallel with respect to the light traveling from the lower right to the upper left, so the LCD was observed from the left side. In some cases it looks black. On the other hand, for light traveling from the lower left to the upper right, since the liquid crystal molecules are aligned vertically, when the LCD is observed from the right side, it appears close to white. As described above, the LCD described above has a drawback that the display state depends on the viewing angle.

  As a method of widening the viewing angle, the liquid crystal molecular long axis is aligned in the direction perpendicular to the substrate when no voltage is applied, resulting in black display, and when the voltage is applied, the liquid crystal molecular long axis is inclined in the direction parallel to the substrate. A VA (Vertically Aligned) method for displaying white has been proposed (see, for example, Patent Document 1). In the VA system described above, a technique for forming protrusions on the liquid crystal layer has been proposed as means for increasing the viewing angle. Such protrusions are formed to control the alignment of the liquid crystal and are referred to as liquid crystal alignment control protrusions. The liquid crystal alignment control protrusion locally gives an inclination to the alignment state of the liquid crystal molecules along the surface thereof, so that the liquid crystal surface can be viewed from the front even when observed obliquely with respect to the liquid crystal surface. The viewing angle can be expanded so that a display state similar to that observed can be obtained.

As shown in FIG. 9 (1) of Patent Document 1 below, the liquid crystal molecule major axis is aligned perpendicular to the substrate surface when no voltage is applied. When an intermediate voltage is applied, the major axis of the liquid crystal molecules slightly tilts from the state in which no voltage is applied, as shown in FIG. At this time, the inclination direction of the liquid crystal molecule major axis is determined by the influence of the inclined portion of the protrusion, and the alignment direction of the liquid crystal is divided in the middle of the protrusion (protrusion 20 in FIG. 9 of Patent Document 1 below) and the electrode slit. At this time, for example, the light transmitted from directly below to above is slightly affected by the birefringence because the major axis of the liquid crystal molecules is slightly inclined, so that the transmission is suppressed and a gray halftone display is obtained. Further, light transmitted from the lower right to the upper left is difficult to transmit in the region where the liquid crystal molecule long axis is inclined in the left direction, and very easily transmitted in the region inclined in the right direction. For this reason, on average, a gray halftone display is obtained.
On the other hand, light transmitted from the lower left to the upper right is also displayed in gray on the same principle, and uniform display can be obtained in all directions. Further, when a predetermined voltage is applied, the major axis of the liquid crystal molecules becomes almost horizontal, and white display can be obtained in all directions. As described above, in the VA system, display with little viewing angle dependency can be obtained in all of the black, halftone, and white display states.

  As described above, in order to divide the alignment direction of the long axis of the liquid crystal molecule and to perform a display with a wide viewing angle, flickering and non-uniformity, the liquid crystal control protrusion preferably satisfies the following conditions. Here, “flickering” means a change when a signal that changes the brightness or color of the display uniformly (for example, a signal that changes in the order of “full black”, “full white”, and “full black”) is sent. The state of is not uniform. Further, “unevenness” refers to display non-uniformity observed when a uniform still image signal (for example, a full-surface gray still image signal) is sent. Note that “flickering” and “unevenness” do not have a fatal effect on the display of normal movies and characters, so they cannot be said to be bad products. And “unevenness” are conspicuous, it is judged as a poor product.

  The first condition is that the relative dielectric constant of the liquid crystal alignment control protrusion is lower than the relative dielectric constant of the liquid crystal. The relative dielectric constant of the liquid crystal is about 10 (see, for example, paragraph 113 of Patent Document 1). If the relative dielectric constant of the liquid crystal alignment control protrusion is higher than the relative dielectric constant of the liquid crystal, the liquid crystal cannot be driven normally, causing flickering. Note that “the liquid crystal is normally driven” means that liquid crystal molecules aligned perpendicular to the substrate when no voltage is applied are divided and aligned as designed along with the application of voltage between the electrodes.

The second condition is that the surface of the protrusion is smooth (no irregularities). If the surface of the protrusion is not smooth, the alignment of the liquid crystal molecules is disturbed, causing display unevenness.
By using the liquid crystal alignment control protrusion satisfying these conditions, it is possible to perform display without flickering or unevenness at a wide viewing angle.

  However, when no voltage, which is black, is applied, the portion indicated by each arrow S as shown in the sloped portions of the protrusions (FIGS. 1 (1) to (3) and (5) to (6)) is inherent. The major axis of liquid crystal molecules to be aligned in the direction perpendicular to the substrate is tilted and aligned. Conventionally, liquid crystal alignment control protrusions that transmit visible light have been manufactured (see, for example, Patent Document 2), and thus light leakage occurs from the inclined portion of the liquid crystal alignment control protrusions. As a result, the contrast is lowered.

  In order to solve this problem, means for improving the contrast by making the liquid crystal alignment control protrusions with a material that does not allow visible light to pass therethrough has been suggested (for example, see Patent Document 1). However, specifically required transmission optical density (OD) and prescription are not disclosed, and specific chromaticity is not disclosed.

  In addition, liquid crystal alignment control protrusions containing conductive particles are disclosed for improving image sticking, and carbon black is cited as an example of the conductive particles. And the dielectric constant is not disclosed (for example, see Patent Document 3).

  Further, although a method for producing a liquid crystal alignment control protrusion containing carbon black is disclosed, the liquid crystal display device provided with the liquid crystal alignment control protrusion is described as having a disordered liquid crystal alignment in the vicinity of the protrusion. (For example, refer to Patent Document 4).

  Thus, producing projections using only carbon black is not preferable because it often causes display unevenness. This is thought to be because carbon black is likely to agglomerate, fuzzy and smoothness of the projection surface cannot be obtained, and the alignment of the liquid crystal is disturbed.

  In view of the above, there has been a demand for a liquid crystal alignment control protrusion capable of achieving stable liquid crystal driving and alignment and preventing light leakage, and a material and manufacturing method capable of achieving it.

Japanese Patent No. 2947350 JP 2003-330011 A JP 2003-15276 A Japanese Patent No. 3255107

An object of the present invention is to solve the above-described conventional problems and achieve the following objects. That is, the present invention relates to a liquid crystal alignment control protrusion without light leakage, a composition for producing the same, a resin transfer material, a method for manufacturing a protrusion for a liquid crystal display device using these, a substrate for a liquid crystal display device, An object is to provide a liquid crystal display element.
A further object of the present invention is to provide a liquid crystal display device having a high viewing angle and a high contrast without display unevenness, using the liquid crystal alignment control protrusion.

Means for solving the problems are as follows. That is,
<1> A projection for controlling alignment of liquid crystal molecules used for alignment control of liquid crystal molecules, and a deviation from an achromatic point (x = 0.333, y = 0.333) of chromaticity is ΔE within 30, And containing fine metal particles and a colorant ,
The metal fine particles have a number average particle size of 10 to 150 nm,
The metal forming the metal fine particles contains at least one of silver, gold, tin, nickel, platinum, and cobalt,
The metal fine particle content in the protrusion for controlling liquid crystal alignment is 0.5 to 9.0% by volume,
A protrusion for controlling liquid crystal alignment, characterized in that the relative dielectric constant is 2.0 to 6.0 .

  <2> The liquid crystal alignment according to <1>, wherein the metal fine particles are at least one selected from metal fine particles, alloy fine particles, metal compound fine particles, and composite fine particles of a metal and a metal compound. This is a control projection.

  <3> The liquid crystal alignment control protrusion according to <1> or <2>, wherein the colorant is carbon black and / or a pigment other than carbon black.

  <4> The liquid crystal alignment control protrusion according to <1> to <3>, wherein a mass ratio of the metal fine particles (x) to the colorant (y) is 0.1 to 10. .

  <5> The liquid crystal alignment control protrusion according to <1> to <4>, wherein the optical density is 0.3 or more and 10 or less.

< 6 > The liquid crystal alignment control protrusion according to <1> to < 5 >, wherein the metal fine particles are silver fine particles.

< 7 > The liquid crystal alignment control protrusions according to <1> to <6>, wherein the cross-sectional shape is ridge-like.

< 8 > A composition used for producing the liquid crystal alignment control protrusions according to <1> to < 7 >, wherein at least (A) metal fine particles, (B) a colorant, (C) an alkali-soluble resin, (D) A polymerizable monomer and (E) a photopolymerization initiator or a photopolymerization initiator system.

< 9 > A resin transfer material having a resin transfer material having at least one resin layer on a temporary support, wherein the resin layer includes the composition of < 8 >. Material.

< 10 > A method for producing a protrusion for controlling liquid crystal alignment, comprising a step of attaching the resin transfer material of < 9 > to a substrate with a laminator.

< 11 > A method for producing a liquid crystal alignment control protrusion, comprising a step of applying the composition of < 8 > with a slit nozzle.

< 12 > A substrate for a liquid crystal display device, comprising the liquid crystal alignment control protrusions of <1> to < 7 >.

< 13 > A liquid crystal display element comprising the substrate for a liquid crystal display device according to < 12 >.

< 14 > A liquid crystal display device comprising the substrate for a liquid crystal display device according to < 12 >.

According to the present invention, a liquid crystal alignment control protrusion without light leakage, a composition for producing the same, a resin transfer material, a method for manufacturing a protrusion for a liquid crystal display using the same, and a substrate for a liquid crystal display A liquid crystal display element can be provided.
Furthermore, according to the present invention, it is possible to provide a liquid crystal display device having a high viewing angle and a high contrast without display unevenness using the liquid crystal alignment control protrusion.

  Hereinafter, the liquid crystal alignment control protrusion of the present invention will be described in detail.

《LCD alignment control protrusions》
The liquid crystal alignment control protrusion of the present invention is a liquid crystal alignment control protrusion used for controlling the alignment of liquid crystal molecules, and the deviation of the chromaticity from the achromatic point (x = 0.333, y = 0.333). ΔE is within 30, and (1) contains metal fine particles and (2) a colorant, and the metal fine particles have a number average particle diameter of 10 to 150 nm, and form the metal fine particles. The metal contains at least one of silver, gold, tin, nickel, platinum, and cobalt, and the metal fine particle content in the protrusion for controlling liquid crystal alignment is 0.5 to 9.0% by volume, and the dielectric constant The rate is 2.0 to 6.0 .
The projection for controlling the liquid crystal display of the present invention can obtain stable liquid crystal alignment and normal liquid crystal drive, prevent light leakage, and improve the display quality and the contrast of the liquid crystal display device. It aims at reduction.

The liquid crystal alignment control protrusion of the present invention (hereinafter sometimes simply referred to as “protrusion”) has a chromaticity deviation from an achromatic point (x = 0.333, y = 0.333) within Δ30 of ΔE In other words, by setting it to black, it is possible to block or attenuate some light leakage that has occurred in the vicinity of the liquid crystal alignment control protrusions, and to improve display contrast when incorporated in a liquid crystal display device. it can. Moreover, contrast can be further improved by setting it as optical density (OD) 0.3-10. From such a viewpoint, it is preferable that the optical density (OD) of the liquid crystal alignment control protrusion of the present invention is 0.3 or more and 10 or less.
Furthermore, light leakage can be further attenuated if the vertical cross-sectional shape of the protrusion is like a bowl.

  The liquid crystal alignment control protrusion of the present invention uses metal fine particles and a colorant to make the protrusion black. Thereby, the surface of the liquid crystal alignment control protrusion can be made smoother (no irregularities) than when only the colorant is used, and the liquid crystal can be stably aligned. As a result, display unevenness can be reduced when incorporated in a liquid crystal display device. Further, by using the colorant, the chromaticity can be easily adjusted, and the chromaticity shift from the achromatic color point can be easily reduced.

Furthermore, by reducing the relative dielectric constant of the liquid crystal alignment control protrusion of the present invention (at least by making it smaller than the relative dielectric constant of the liquid crystal), the liquid crystal can be driven normally and display flicker is reduced. Can do. From such a viewpoint, the relative dielectric constant of the liquid crystal alignment control protrusion of the present invention is 2.0 to 6.0.

Hereinafter, the liquid crystal alignment control protrusion of the present invention will be described in detail.
The deviation from the achromatic point (x = 0.333, y = 0.333, Y is the same value as the sample) is ΔE within 30 in the liquid crystal alignment control projection of the present invention. Hereinafter, a color whose deviation from the achromatic color point (x = 0.333, y = 0.333, Y is equal to the sample) is ΔE and within 30 is referred to as “black”.

The chromaticity is measured with a C light source, and x, y, and Y are calculated. When calculating the chromaticity deviation from the achromatic color point, the calculation is performed assuming that the Y of the achromatic color point is equal to the Y of the sample. The chromaticity shift is more preferably 20 or less, still more preferably 15 or less, and most preferably 10 or less. If the color difference exceeds 30, it is not preferable because light leakage occurs and the contrast is lowered or the screen is colored during black display.
In addition, metal fine particles are generally colored, but there are many cases where the deviation from the achromatic point is large. In the present invention, the metal fine particles can be blackened by mixing a coloring material having absorption in a wavelength region where there is no absorption. As described above, since the liquid crystal alignment control protrusion of the present invention can adjust the chromaticity by selecting an appropriate colorant, the chromaticity shift (ΔE) can be easily reduced.

  The “optical density (OD)” in the present invention means a transmission optical density at a wavelength of 555 nm unless otherwise specified. The transmission optical density (OD) at a wavelength of 555 nm of the liquid crystal alignment control protrusion of the present invention is preferably 0.3 or more and 10 or less, more preferably 1.0 or more and 6.0 or less from the viewpoint of shielding light leakage. Yes, more preferably 1.5 or more and 6.0 or less, and particularly preferably 2.0 or more and 6.0 or less. If the optical density (OD) of the protrusions is less than 0.3, light leakage may occur and the contrast may be lowered. Further, the larger the optical density (OD), the smaller the light leakage, which is preferable. However, in consideration of costs such as material costs for manufacturing the liquid crystal alignment control protrusion, the optical density is 6.0 or less. Is preferred.

  For the actual measurement of both the chromaticity and the optical density, a layer having the same thickness as that for forming the liquid crystal alignment control projection of the present invention was formed on the transparent substrate using the material for forming the liquid crystal alignment control projection of the present invention. A film-like sample for measurement can be formed through the same process as the liquid crystal alignment control protrusion of the present invention except that the pattern is not exposed, and measurement can be performed using this.

As described above, the relative dielectric constant of the liquid crystal alignment control protrusion of the present invention is preferably less than or equal to the relative dielectric constant of the liquid crystal material, and more preferably 1.0 or more and 9.0 or less. Is 2.0 to 6.0, more preferably 2.0 to 4.0, and most preferably 2.0 to 3.0. Protrusions having a relative dielectric constant of less than 1 are difficult to produce because there is currently no material with a relative dielectric constant of less than 1. Further, when the relative dielectric constant is 9 or less, normal liquid crystal driving is ensured and flickering can be suppressed. The relative dielectric constant of the liquid crystal alignment control protrusion of the present invention is 2.0 to 6.0.
Here, the “relative permittivity (ε)” in the present invention is the ratio of the dielectric constant of the protrusion to the vacuum dielectric constant. In the actual measurement, as in the case of the measurement of chromaticity and optical density, a measurement sample is formed, and the capacitance of the capacitor obtained by sandwiching the sample with electrodes is measured, and the relative dielectric constant (ε ) Can be calculated.

When the vertical cross-sectional shape of the liquid crystal alignment control protrusion of the present invention is 蒲 鉾, more stable alignment can be obtained, leading to reduction in display unevenness.
In the present invention, “蒲 鉾” means that the arc formed by the image of the liquid crystal alignment control protrusion intersects the substrate (the uppermost ITO surface) in the liquid crystal alignment control protrusion having a cross section as shown in FIG. When the points and B points are used, the following points (i) to (iv) are applicable.
(I) The angle (x in FIG. 2) at which the arc intersects the substrate (top ITO) at point A is 90 ° or less (ii) The angle at which the arc intersects the substrate (top ITO) at point B (in FIG. 2) y) is 90 ° or less. (iii) A region of ½ or more of the length of the arc AB protrudes on the opposite side of the substrate. (iv) On the arc AB, 2/10 of the length of the arc AB. If the position moved to the point is point C, and the position moved from point A to point B by 8/10 of the length of the arc AB on the arc AB is point D, the radius of curvature of the arc CD (lines CP and DP) FIG. 3 shows a specific example (SEM image) of the liquid crystal alignment control protrusion having a cross-sectional shape that is 1/3 or more of the line segment AB over the entire area of the arc CD.

  When the photosensitive resin composition for forming protrusions for controlling liquid crystal alignment has a light-shielding property, it does not completely cure to the lower part during exposure, the lower part dissolves during the subsequent development process, and further in the subsequent baking process. It is possible to easily obtain the above-described protrusion for controlling liquid crystal alignment. Conversely, in order to produce a conventional box-shaped or trapezoidal liquid crystal alignment control protrusion, a known method such as increasing the exposure amount at the time of exposure or including a chemical amplification agent in the photosensitive resin composition However, it may be difficult to form with high accuracy, such as an increase in line width.

  In addition, if the photosensitive resin composition has a transmission optical density of exposure light of 0.3 or more when it is used as a liquid crystal alignment control protrusion, the liquid crystal alignment control protrusion of the present invention in the above-described steps is used. Can be easily obtained. Therefore, in order to produce a ridge-like projection for controlling liquid crystal alignment according to the present invention, it is preferable that the transmission optical density of exposure light of the projection for controlling liquid crystal alignment is 0.3 or more. When the transmission optical density of the exposure light is 0.3 or more, curing due to exposure can be prevented from proceeding excessively. When the transmission optical density of the exposure light is less than 0.3, an ultraviolet absorber described later can be contained in order to make the transmission optical density of the exposure light 0.3 or more.

<Metallic fine particles>
The liquid crystal alignment control protrusion of the present invention includes metal fine particles.
In the present invention, “fine particles” mean particles having a major axis length of 1 μm or less. The shape is not particularly limited.
In the present invention, “metals” refers to an inorganic substance containing a metal element in its composition element, and “metal fine particles” refers to fine particles composed of the metals. Moreover, the metal fine particles include those having different compositions depending on the site.

  The metal fine particles in the present invention are preferably at least one selected from metal fine particles, alloy fine particles, metal compound fine particles, and composite fine particles of metal and metal compound.

~ Metallic fine particles ~
The “metal” in the present invention is a substance composed of the following elements. That is, in the long period periodic table (IUPAC 1991), the second period 1 to 13 group, the third period 1 to 14 group, the fourth period 1 to 14 group, the fifth period 1 to 15 group, the sixth period 1 to 16 group It is a substance composed of these elements. “Metal fine particles” are fine particles composed of the metal.
The metal constituting the metal fine particles in the present invention is preferably a metal capable of forming fine particles. The metal forming the fine particles is preferably a metal of the fourth to sixth periods of the long-period periodic table (IUPAC 1991) and a group 4-14. Among these, silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, tungsten, manganese, or titanium is preferable, among which silver, gold, tin, nickel, platinum, or cobalt is preferable, In particular, silver is particularly preferable from the viewpoint of cost and stability. The metal fine particles in the present invention may be used alone or a mixture of two or more kinds of metal fine particles. In the present invention, the metal constituting the metal fine particles is silver, gold, tin, nickel, platinum, or cobalt.

As the metal fine particles, commercially available ones can be used, and they can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
In the case of silver fine particles (colloidal silver), a conventionally known method, for example, a method of reducing a soluble silver salt with hydroquinone in an aqueous gelatin solution disclosed in US Pat. No. 2,688,601, Germany A method of reducing a sparingly soluble silver salt described in Patent No. 1,096,193 with hydrazine, a method of reducing to silver with tannic acid described in US Pat. No. 2,921,914 As described above, a method of chemically reducing silver ions in a solution, a method of forming silver particles by electroless plating described in JP-A-5-134358, a bulk metal in an inert gas such as helium It is possible to use a method such as a gas evaporation method that evaporates and cold traps with a solvent.

~ Alloy fine particles ~
The “alloy” in the present invention is a substance composed of two or more different metals, or a mixture of a metal and a nonmetal (a substance not containing a metal element). The “alloy fine particles” are fine particles made of the alloy. The alloy fine particles include those having different compositions depending on the site.

  The alloy constituting the alloy fine particles in the present invention is preferably an alloy capable of forming fine particles. The metal forming the alloy is preferably at least two metals selected from Group 4 to Group 14 metals of the Long-Term Periodic Table (IUPAC 1991). Among these, at least two kinds of metals selected from silver, nickel, cobalt, iron, copper, palladium, gold, platinum, tin, zinc, tungsten, manganese, or titanium are preferable. Among them, silver, nickel More preferably, at least two metals selected from iron, copper, palladium, gold, platinum, tin, zinc, tungsten, manganese or cobalt, especially silver and nickel, silver and iron, silver and copper, Silver and palladium, silver and gold, silver and platinum, silver and tin, silver and gold, silver and tin, gold and nickel, gold and iron, gold and copper, gold and palladium, gold and platinum, gold and tin, platinum and Nickel, platinum and iron, platinum and copper, platinum and palladium, platinum and tin, gold and silver and copper, gold and silver and platinum, gold and silver and iron, gold and silver and tin, gold and copper and platinum, gold and Copper and iron, gold and copper and tin, gold and Gold and iron, gold and platinum and tin, gold and iron and tin, silver and copper and platinum, silver and copper and iron, silver and copper and tin, silver and platinum and iron, silver and platinum and tin, copper and platinum and An alloy composed of iron, copper, platinum and tin, or platinum, iron and tin is particularly preferable from the viewpoint of stability and color tone. The alloy fine particles in the present invention may be used alone or a mixture of two or more kinds of alloy fine particles.

  The alloy fine particles can be commercially available, or can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.

~ Metal compound fine particles ~
The “metal compound” in the present invention is a compound composed of the metal and a nonmetal. The “metal compound fine particles” are fine particles composed of the metal compound. The metal compound fine particles include those in which two or more kinds of metal compounds are formed into one fine particle. Moreover, the thing from which a composition changes with parts is also contained.

Examples of the compound of metal and nonmetal include metal oxide, sulfide, nitride, carbide (carbide), sulfate, carbonate and the like. Of these, oxides and sulfides are particularly preferable from the viewpoint of color tone and ease of forming fine particles. Examples of these metal compounds include copper sulfide (II), iron sulfide, silver sulfide, cobalt oxide (Co ₃ O ₄ , CoO), copper oxide (CuO, Cu ₂ O), iron oxide, manganese oxide (Mn ₃ O ₄ , MnO _2, etc.), titanium black (titanium oxide), etc., but silver sulfide, cobalt oxide, copper oxide, iron oxide, manganese oxide, titanium black have color tone, ease of fine particle formation and stability From the viewpoint of The metal compound fine particles in the present invention may be used singly or as a mixture of two or more kinds of metal compound fine particles.

  As the metal compound fine particles, commercially available ones can be used, and they can be prepared by oxidation or sulfidation of metal ions. The metal oxide fine particles can be prepared by a DC arc plasma method as disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2002-114521 and 2002-104828. The metal sulfide fine particles can be prepared by sulfiding a metal salt.

-Composite fine particles of metal and metal compound-
The “composite fine particles of metal and metal compound” in the present invention are those in which the metal and the metal compound are formed into one fine particle. Moreover, the thing from which a composition changes with parts is also contained. Examples of the composite fine particles of metal and metal compound include those in which the inside of the particle is a metal and the surface is a metal compound. Further, the metal and the metal compound may be one kind or two kinds or more, respectively. Examples of composite fine particles of metal and metal compound include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, composite fine particles of tin and tin sulfide, and composite fine particles of cobalt and cobalt oxide. , Etc.

-Core shell-
Further, the composite fine particles of the metal and the metal compound may be core-shell type composite particles. The core-shell type composite particles are obtained by coating the surface of a core material with a shell material. There is no restriction | limiting in particular in the preparation methods of the composite fine particle which has a core-shell structure, The following are mentioned as a typical method.

(1) A method of forming a metal compound shell on the surface of metal fine particles produced by a known method by oxidation, sulfurization, etc. For example, metal fine particles are dispersed in a dispersion medium such as water, and sodium sulfide or There is a method of adding a sulfide such as ammonium sulfide. By this method, the surface of the particles is sulfided to form core-shell composite particles.
In this case, the metal fine particles to be used can be produced by a known method such as a gas phase method or a liquid phase method. The method for producing metal fine particles is described in, for example, “Latest Trend II in Technology and Application of Ultrafine Particles II (issued by Sumibe Techno Research Co., Ltd. 2002)”.

(2) A method of continuously forming a metal compound shell on the surface in the process of producing metal fine particles. For example, a reducing agent is added to a metal salt solution to reduce a part of metal ions to form metal fine particles. And then adding a sulfurizing agent to form a metal sulfide around the produced metal fine particles.

(Shape of metal fine particles)
The shape of the metal fine particles in the present invention can be roughly classified into spherical fine particles and shape anisotropic fine particles. However, since the metal fine particles in the present invention can be easily adjusted in chromaticity by using a colorant, the shape of the metal fine particles is not particularly limited.
-Shape anisotropic fine particles-
“Shape anisotropy” in the present invention means that at least one of the length L, width b, height or thickness t of the box is different, and excludes regular side bodies including spheres and cubes. means.
In the above definition, the diameter of the fine particles in the present invention is defined as a triaxial diameter. That is, a box (a rectangular parallelepiped) in which one fine particle can be exactly (contained) is considered, and the size of the fine particle is defined by the length L, width b, height, or thickness t of the box. There are several methods for storing fine particles in a box. In the present invention, the following method is adopted.

First, the fine particles are placed on a flat surface so that the center of gravity is the lowest and stable. Next, fine particles are sandwiched between two parallel flat plates standing at right angles to the plane, and the flat plate interval at the position where the flat plate interval is the shortest is defined as “width b”. Next, fine particles are sandwiched between two parallel flat plates that are perpendicular to the two flat plates that determine the width b and also perpendicular to the flat surface, and the distance between the two flat plates is defined as “length L”. Finally, the top plate is placed parallel to the plane so as to come into contact with the highest position of the fine particles, and the distance between the top plate and the plane is set to the height or thickness t (this method allows the flat plate, two flat plates and A rectangular parallelepiped defined by the board is formed.)
Also, the axis corresponding to the longest triaxial diameters b, L and t of the fine particles is defined as “long axis”, the length in the long axis direction is defined as “long axis length”, and parallel to the long axis. The diameter when the projected area obtained by irradiating fine particles with light is converted into a perfect circle is defined as “short axis length”.

The shape anisotropic fine particles include, for example, a rod shape (a needle shape, a cylindrical shape, a rectangular column shape such as a rectangular parallelepiped, a rugby ball shape, etc.), a flat shape (a scale shape, an elliptical plate shape, a plate shape), a fiber shape, a confetti shape, There are fine particles such as coil and wire. Such shape anisotropic fine particles are superior in hiding power than fine particles not having shape anisotropy.
Although there is no restriction | limiting in particular in the shape of the said shape anisotropic fine particle, From a viewpoint that hiding power is large, rod shape and flat plate shape are preferable, and it is especially preferable that it is flat plate shape.

-Production of shape anisotropic particles-
Commercially available shape anisotropic fine particles can be used. Among these, shape anisotropic metal fine particles can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
In particular, for rod-shaped silver fine particles, spherical silver fine particles are used as seed particles, then silver salt is further added, and a reducing agent having a relatively low reducing power such as ascorbic acid is used in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide). That silver rods and wires can be obtained by Adv. Mater. 2002, 14, 80-82. A similar description is described in Mater. Chem. Phys. 2004, 84, 197-204, Adv. Funct. Mater. 2004, 14, 183-189. Furthermore, as a method using electrolysis, Mater. Lett. 2001, 49, 91-95 and a method for producing silver rods by irradiating microwaves are disclosed in J. Am. Mater. Res. 2004, 19, 469-473. In addition, as an example in which reverse micelle and ultrasonic irradiation are used in combination, J. et al. Phys. Chem. B, 2003, 107, 3679-3683.
The same applies to gold (Au). Phys. Chem. B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709, J. MoI. Am. Chem. Soc. 2002, 124, 14316-14317.
The rod-shaped particles can be formed by improving the above-described method (addition amount adjustment, pH control). A method for forming tabular silver particles by using reverse micelles and ultrasonic irradiation in combination is described in J. Org. Phys. Chem. B, 2003, 107, 2466-2470.

The number average particle diameter of the metal fine particles in the present invention is not particularly limited as long as it does not exceed the film thickness, but is preferably in the range of 1 nm to 1000 nm, more preferably in the range of 5 nm to 500 nm, and still more preferably in the range of 10 to 150 nm. .
When the number average particle diameter of the metal fine particles is in the range of 1 nm to 1000 nm, the production is easy, the aggregation of the particles can be prevented and the formation of secondary particles can be prevented, and the dispersion stability can be improved. It is good. The number average particle diameter of the metal fine particles in the present invention is 10 to 150 nm.
The term “particle diameter” as used herein refers to the diameter when the electron micrograph image of the fine particles is a circle of the same area, and the “number average particle diameter” refers to the particle diameter described above for a large number of particles. And mean the average value of these 100.

The metal fine particle content in the projection for controlling liquid crystal alignment of the present invention is 0.5 to 9.0% by volume , more preferably 1.0 to 7.0% by volume, and still more preferably 1.5. When the content of fine particles in the protrusion is in the range of 0.5 to 9.0% by volume, light leakage can be prevented, contrast can be improved, and the relative dielectric constant can be increased. Can be small.
Actually, it is preferable that the fine particle content of the protrusion satisfies that the protrusion OD is 0.3 or more, the protrusion has a relative dielectric constant of 9 or less, and has suitability for production and developability. Accordingly, the upper and lower limits of the fine particle content depend on the type of fine particles.
Further, the projection for controlling the alignment of liquid crystal according to the present invention contains 0.5% by volume or more of metal fine particles and / or alloy fine particles as the metal fine particles, thereby suppressing the occurrence of image sticking.

<Colorant>
~ Coloring material ~
The liquid crystal alignment control protrusion of the present invention contains a colorant together with the above-mentioned metal fine particles.
The “colorant” in the present invention means a colored substance excluding the “metal fine particles”, and the dielectric constant of the liquid crystal alignment control protrusions does not exceed the dielectric constant (about 10) of the liquid crystal, and is suitable for production. It is preferable to satisfy the condition that the color is black and can be realized by combining with the “metal fine particles”. Examples of the colorant include carbon black, pigments other than carbon black, and dyes. These may be used alone or in combination. The colorant in the present invention is preferably carbon black and / or a pigment other than carbon black.

  Preferable examples of these colorants include Fat Black HB (CI 26150), Monolite First Black B (CI Pigment Black 1), carbon black, and JP-A-7-28236. [0015] to [0027].

  The pigment and dye generally have a number average particle diameter of 5 μm or less, preferably 1 μm or less, and more preferably 0.5 μm or less.

Further, the mass ratio (x / y) of the content (x) of the metal fine particles and the content (y) of the colorant is such that the concealing power is increased with the metal fine particles and the color tone is adjusted with the colorant. From this viewpoint, 0.1 to 10 is preferable, and 0.3 to 4 is more preferable.
In addition, since the color of the metal fine particles changes depending on the material, shape, and size, it is preferable to make the metal fine particles black by combining the colorants that exhibit complementary colors.

<Arrangement mode>
First, the basic arrangement of the liquid crystal alignment control protrusions according to the present invention will be described with reference to FIG. FIG. 4 is a schematic cross-sectional view for explaining the liquid crystal alignment control protrusion of the present invention.
The liquid crystal control protrusion of the present invention regulates the alignment direction of the liquid crystal that is obliquely aligned when a voltage is applied in the VA method. For example, as shown in FIG. 1 is formed on the surfaces of the electrode 2 and the electrode 3. The electrode 2 and the electrode 3 are configured to sandwich the liquid crystal layer 4, and the liquid crystal molecules 5 are aligned in the liquid crystal layer 4. Among the liquid crystal molecules 5, the liquid crystal molecules 5 in the vicinity of the liquid crystal alignment control protrusion 1 are aligned along the shape of the liquid crystal alignment control protrusion 1. Further, as shown in FIG. 4B, the liquid crystal alignment control protrusion 1 may be formed only on the surface of the electrode on one side. In FIG. 4B, the liquid crystal alignment control protrusion 1 is formed only on the surface of the electrode 3, and an electrode having a slit for controlling liquid crystal alignment is used as the electrode 6 of the upper substrate.
Thus, by regulating the orientation of the liquid crystal molecules 5, it is possible to ensure visual characteristics that do not depend on the observation position (viewing angle) with respect to the liquid crystal surface. In addition, the arrangement | positioning aspect is not restricted to these, The arrangement | positioning which a viewing angle spreads can be selected suitably.

  The arrangement mode of the liquid crystal alignment control protrusions in the present invention can be appropriately selected from known modes. For example, it can be formed in the mode described in Japanese Patent No. 2947350. For example, a plurality of columnar bodies formed in a strip shape on a substrate and having a cross-sectional shape perpendicular to the length direction are arranged in a pattern extending in parallel in one direction at an equal pitch, and each of the two substrates A linear pattern provided on the conductive layer is preferable (see FIG. 15 of Japanese Patent No. 2947350). When the liquid crystal alignment control protrusions of the present invention are provided on the conductive layer substrates of both substrates, it is not always necessary to form liquid crystal alignment control protrusions having the same shape. May be formed.

The liquid crystal alignment control protrusion formed in a strip shape on the substrate (or color filter) is not limited to a linear shape, and may be provided in a bent shape at a predetermined angle (Japanese Patent No. 2947350). 42 and 55 etc.).
In addition, the liquid crystal alignment control protrusion of the present invention can be formed in a dot pattern. In this case, it is preferable in that the liquid crystal is multi-divided and oriented in all directions of 360 ° and the viewing angle is very wide.
In addition, for details on the size, arrangement interval, arrangement shape, and the like of the liquid crystal alignment control protrusions, the description in Japanese Patent No. 2947350 can be referred to.

  In general, a liquid crystal display device using the liquid crystal alignment control protrusion according to the present invention includes a color filter-side substrate including a color filter and a conductive layer (electrode) on the color filter, and a conductive layer ( A liquid crystal layer is sandwiched between two substrates (an electrode) and a counter substrate (a driving element such as a thin film transistor (TFT) may be provided on either the color filter side substrate or the counter substrate). The projection for controlling liquid crystal alignment according to the present invention can be formed using a photosensitive resin layer coating liquid or a resin transfer material described later, on at least one of the conductive layers provided on the two substrates, It is provided as a black liquid crystal alignment control protrusion that is convex on the liquid crystal layer side. By providing the liquid crystal alignment control projection of the present invention, the orientation direction of the liquid crystal molecules can be regulated, and visual characteristics independent of the observation position (viewing angle) with respect to the liquid crystal surface can be ensured.

  Further, the liquid crystal alignment control protrusion of the present invention is applied to a liquid crystal display device without a color filter (a device for monochrome display or a field sequential type device that displays while changing the color of the backlight in a short time). You can also

"Composition"
The projection for controlling liquid crystal alignment of the present invention comprises at least (A) metal fine particles, (B) colorant, (C) alkali-soluble resin, (D) polymerizable monomer, and (E) photopolymerization initiator or photopolymerization start. It can be formed by photolithography using a composition containing an agent system (a photosensitive resin composition for protrusions for controlling liquid crystal alignment (hereinafter sometimes referred to as “the composition of the present invention” as appropriate)).
As the metal fine particles (A), the metal fine particles described above are used, and the metal fine particles are selected from metal fine particles, metal compound fine particles, alloy fine particles, and composite fine particles of metal and metal compound. At least one is preferred. The composition of this invention is formed from the photosensitive resin composition which contains another component further as needed. The above-mentioned colorant is also used as the colorant (B), and the colorant is preferably carbon black and / or a pigment other than carbon black.

(C) Alkali-soluble resin As the alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) in the present invention, a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. 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. Particularly preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid, and other Mention may be made of multicomponent copolymers with monomers. These polymers having a polar group may be used alone, or may be used in the state of a composition used in combination with an ordinary film-forming polymer.
The content of the alkali-soluble resin relative to the total solid content of the composition of the present invention is generally 20 to 50% by mass, and preferably 25 to 45% by mass.

(D) Polymerizable monomer The polymerizable monomer in the invention is preferably a polymerizable monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such a polymerizable monomer include a compound 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 of the polymerizable monomer 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, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate Rate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerol tri (meth) acrylate; trimethylolpropane and glycerol Examples thereof include polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as (meth) acrylate.

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 polymerizable monomers may be used alone or in combination of two or more.
As for content of the said polymerizable monomer with respect to the total solid of the composition of this invention, 5-50 mass% is common, and 10-40 mass% is preferable.

(E) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system in the present invention, a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, US The acyloin ether compounds described in Japanese Patent No. 2448828, the aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. Nos. 3,046,127 and 2,951,758 No. 3,549,367, a combination of a triarylimidazole dimer and a p-aminoketone, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and a trihalomethyl- s-triazine compounds described in US Pat. No. 4,239,850 A trihalomethyl - 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 composition of the present invention is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

(Other additives)
-Solvent-
In the composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

-Surfactant-
In the composition of the present invention, an appropriate surfactant can be contained in the composition from the viewpoint of being able to control to a uniform film thickness and effectively preventing coating unevenness (color unevenness due to film thickness fluctuation). preferable.
Suitable examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.

-Thermal polymerization inhibitor-
The composition of the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-UV absorber-
The composition of the present invention may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like.
Further, by using the ultraviolet absorber as described above, the transmission optical density with respect to the exposure light can be adjusted to 0.3 or more in order to form the liquid crystal alignment control protrusions in a bowl-like manner.

-Binder-
A thermoplastic binder can be used in the composition of the present invention. The addition amount of the binder is appropriately determined within a range not impairing the effects of the present invention. Furthermore, an additive for plasticizing the resin to be used (alkali-soluble resin) can be added to the composition of the present invention as necessary.

Further, in the composition of the present invention, in addition to the additives, other additives such as an adhesion aid, a thermoplastic binder and a plasticizer described in JP-A-11-133600 are contained. be able to.
Examples of the thermoplastic binder include known binders such as ethylenically unsaturated compounds. The addition amount of the binder is appropriately determined within a range not impairing the effects of the present invention.
Examples of the plasticizer include glycerin, ethylene glycol, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate, alkylphenol, tricresyl phosphate Etc. The addition amount of the plasticizer is preferably 0 to 10% by mass, and more preferably 1 to 8% by mass with respect to the total amount of the resin.

<Formation of projection for controlling liquid crystal alignment>
The protrusion for controlling liquid crystal alignment of the present invention basically has (1) resin transfer in which a resin layer containing the composition of the present invention (photosensitive resin composition) is provided as a photosensitive resin layer on a temporary support. A method of forming a protrusion for controlling liquid crystal alignment comprising a photosensitive resin layer on the inner side of the conductive layer (particularly between the substrate and the conductive layer) by transfer, and (2) the composition of the present invention (photosensitive resin composition) And a liquid prepared by coating a substrate (or color filter) on the substrate (or color filter) to form a photosensitive resin layer directly on the conductive layer, and forming a liquid crystal alignment control protrusion comprising the layer, 3) A liquid prepared containing the composition (photosensitive resin composition) of the present invention is ejected directly onto the conductive layer in the form of a strip or dots on the substrate (or color filter) by an inkjet method. Thereby forming a liquid crystal alignment control protrusion. Law, and the like. When forming a layer by applying a liquid containing a photosensitive resin composition (hereinafter sometimes referred to as “photosensitive resin layer coating liquid”) on a temporary support or a substrate (color filter). A known coating method such as a spin coating method can be applied.
In the present invention, the method (1) is preferable in that it is easy to form a structure having a uniform thickness. First, the method (1) and the resin transfer material used in the method will be described.

<Resin transfer material>
The liquid crystal alignment control protrusion of the present invention can be produced by transferring the resin transfer material of the present invention. The resin transfer material is preferably formed using a resin transfer material described in JP-A-5-72724, that is, an integral film. As an example of the structure of the integral film, there may be mentioned a structure in which a temporary support / thermoplastic resin layer / intermediate layer / resin layer / protective film are laminated in this order.
In addition, the resin transfer material of this invention can provide a resin layer by using the above-mentioned composition of this invention.

(Temporary support)
The temporary support for the transfer material needs to be flexible and not to cause significant deformation, shrinkage, or elongation even under pressure or pressure and heating. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.
Although there is no restriction | limiting in particular in the thickness of a temporary support body, the range of 5-200 micrometers is common, and especially the thing of the range of 10-150 micrometers is advantageous from points, such as ease of handling and versatility, and preferable. In addition, the temporary support may contain dyed silicon, alumina sol, chromium salt, zirconium salt and the like. Further, the temporary support may be transparent, translucent or opaque.

(Thermoplastic resin layer)
The component used in the thermoplastic resin layer is preferably an organic polymer described in JP-A-5-72724, and is a polymer according to the Viker Vicat method (specifically, an American material testing method ASTM D1 ASTM D1235). It is particularly preferred that the softening point by the softening point measuring method is selected from organic polymer substances having a temperature of about 80 ° C. or lower. 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 ( Vinyl toluene copolymer such as meth) acrylate or saponified product thereof, poly (meth) acrylate ester, (meth) acrylate copolymer of butyl (meth) acrylate and vinyl acetate, vinyl acetate Copolymer nylon, Copolymer nylon, N-Arco Shimechiru nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

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

(Protective film)
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 it must be easily separated from the resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

(Production method of resin transfer material)
The resin transfer material of the present invention is provided with a thermoplastic resin layer by applying a coating solution (thermoplastic resin coating solution) in which the additive for the thermoplastic resin layer is dissolved on a temporary support, followed by drying. The composition of the present invention (photosensitive resin composition) prepared so that an intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied on the thermoplastic resin layer, dried, and then the intermediate layer is not dissolved. ) Is applied and dried to provide the resin layer.
Also, by preparing a sheet provided with a thermoplastic resin layer and an intermediate layer on the temporary support, and a sheet provided with a resin layer on a protective film, and bonding them together so that the intermediate layer and the resin layer are in contact with each other In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a resin layer and an intermediate layer on a protective film are prepared. It can also be produced by bonding the layers so that the layers are in contact with each other.
In the resin transfer material of the present invention, the thickness of the resin layer formed using the composition of the present invention (photosensitive resin composition) is preferably 1.0 to 5.0 μm, and preferably 1.0 to 5.0 μm. 4.0 micrometers is more preferable and 1.0-3.0 micrometers is especially preferable.
Further, although not particularly limited, preferred film thicknesses of other layers are 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and 4 to 40 μm for the protective film. Generally preferred.

  In addition, although application | coating in the said manufacturing method can be performed with a well-known coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using a slit-shaped nozzle.

(Slit nozzle)
The resin transfer material can be formed by applying and drying the composition of the present invention by a known coating method. It is preferable to apply by a nozzle. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

(A) Application by coating apparatus (2) A liquid prepared containing the composition (photosensitive resin composition) of the present invention is directly applied on a conductive layer by applying the liquid onto a substrate (or color filter). In the case where a photosensitive resin layer is provided and a liquid crystal alignment control protrusion comprising the layer is formed, the composition of the present invention may be applied by a known coating method such as spin coating, curtain coating, slit coating, The coating can be performed by a dip coating method, an air knife coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion coating method using a popper described in US Pat. No. 2,681,294. In particular, the slit coater described in the section of <Resin transfer material> can be preferably used. Preferred examples of the slit coater are the same as described above. When the resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.0 to 2.0 μm.

(B) Affixing with a laminator By using the resin transfer material of the present invention, a resin layer formed in a film shape is subjected to pressure bonding or thermocompression bonding with a roller or flat plate heated and / or pressed on a substrate to be described later. Can be pasted. 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. The preferred film thickness when the resin layer is formed from the resin transfer material of the present invention is the same as the preferred film thickness described in the section <Resin Transfer Material>.

(substrate)
In the present invention, as the substrate on which the liquid crystal alignment control protrusion is formed, for example, a transparent substrate is used, and a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, and the like. Glass plate or plastic film.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring resin composition or a resin transfer material by giving a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

(Oxygen barrier membrane)
In producing the liquid crystal alignment control protrusion of the present invention, when the photosensitive resin layer is formed by applying the composition of the above-described (2) the present invention, an oxygen blocking film is further provided on the photosensitive resin layer. Thus, the exposure sensitivity can be increased. Examples of the oxygen barrier film include those already described in the section of (Interlayer) of <Resin Transfer Material>. Although not particularly limited, the thickness of the oxygen blocking film is preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate by the methods (1) and (2) described above, and then the mask is interposed through the mask, the thermoplastic resin layer, and the intermediate layer. The liquid crystal alignment control projection of the present invention can be obtained by a process of exposing from above and then developing with a developer.
Here, as the light source for exposure, any light source capable of irradiating light in a wavelength region capable of curing the resin layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-150 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >, More preferably, it is about 10-80 mJ / cm < ² >. An exposure amount of 5 mJ / cm ² or less is not preferable in that the curing does not proceed sufficiently and the formation of liquid crystal alignment control protrusions may not be possible. When the exposure amount exceeds 150 mJ / cm ² , it is not preferable in that curing may proceed wider than a predetermined width (mask width). Furthermore, the liquid crystal alignment control protrusion of the present invention is preferably exposed in a poor oxygen atmosphere. The poor oxygen atmosphere is preferably selected from one or more of at least an inert gas atmosphere, a reduced pressure, or an oxygen barrier layer.
The inert gas may be a general gas such as N ₂ , H ₂ or CO ₂ or a rare gas such as He, Ne or Ar. Among these, N ₂ is preferably used because of safety, availability, and cost. Moreover, under reduced pressure, 0.5 atm or less is preferable, More preferably, the state of 0.1 atm or less is pointed out.
Examples of the oxygen blocking layer include the same ones as described in the above item (oxygen blocking film).

The developer is not particularly limited, and a known developer such as that described in JP-A-5-72724 can be used. The developer preferably has a resin-type developing behavior such as a resin layer. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable, but is further miscible with water. A small amount of an organic solvent having
Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
Further, a known surfactant can be 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.
Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the resin 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 the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
As the cleaning liquid, known ones can be used. Phenoxyoxyethylene surfactant-containing, trade name “T-SD2 (manufactured by Fuji Photo Film)”) is preferable.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

(Bake)
Further, by performing a heat treatment called baking, the liquid crystal alignment control protrusions can be further cured. In addition, by baking, the shape of the liquid crystal alignment control protrusions can be moderately smoothed by contraction of the liquid crystal alignment control protrusions and appropriate flow.

  The baking temperature is preferably 200 to 300 ° C, more preferably 220 to 260 ° C, and most preferably 230 to 250 ° C. The baking time is preferably 10 to 120 minutes, more preferably 20 to 70 minutes, and most preferably 30 to 60 minutes. Thus, by performing the said baking by setting temperature and time, the crosslinking reaction in the photosensitive resin component can advance easily, and productivity can be improved.

《Liquid crystal display device substrate》
The substrate for a liquid crystal display device of the present invention means a substrate in which at least the liquid crystal alignment control protrusion of the present invention is formed on the substrate. The substrate for a liquid crystal display device of the present invention can be suitably used for a liquid crystal display element and a liquid crystal display device described later. Moreover, as the substrate, those described above can be suitably used. The substrate for a liquid crystal display device of the present invention is the liquid crystal alignment control of the present invention by applying the above-described composition of the present invention on the substrate or transferring the resin layer using the resin transfer material of the present invention. Protrusion can be formed.

<Liquid crystal display element>
The liquid crystal display element of the present invention has the substrate for a liquid crystal display device of the present invention. The liquid crystal display element of the present invention is an element having a liquid crystal layer in which a liquid crystal material is sealed between a pair of opposed substrates, and the liquid crystal alignment control protrusion of the present invention is provided as at least one of the substrates. The substrate for a liquid crystal display device of the present invention is used.

<Liquid crystal display device>
The liquid crystal display device of the present invention has the substrate for a liquid crystal display device of the present invention. As described above, the liquid crystal display device of the present invention formed using the substrate for a liquid crystal display device of the present invention has a liquid crystal layer sandwiched between two substrates each having a conductive layer provided on the surfaces facing each other. The liquid crystal alignment control protrusion of the present invention described above can be provided so as to protrude from the conductive layer on the substrate to the liquid crystal layer side. An alignment film can be formed on the conductive layer so as to cover them.

  The basic configuration of the liquid crystal display device of the present invention includes: (1) a driving side in which driving elements such as thin film transistors (hereinafter sometimes referred to as “TFTs”) and pixel electrodes (conductive layers) are arranged; A substrate and a color filter side substrate including a color filter and a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion, (2) the color filter A color filter integrated drive substrate directly formed on the drive side substrate and a counter substrate having a counter electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and a liquid crystal material is sealed in the gap portion. And the like.

Examples of the conductive layer include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; a metal oxide film such as SiO _2. A membrane is particularly preferred. The drive side substrate, the color filter side substrate, and the counter substrate are made of, for example, a known glass plate such as a soda glass plate, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film. Constructed using.

  As the driving side substrate in which driving elements such as TFTs and pixel electrodes are arrayed, for example, TFTs connected to data bus lines and gate bus lines arranged in a matrix so as to cross each other vertically, and TFTs may be used. For example, a conductive layer connected to the data bus line may be provided.

  In any of the above embodiments, a conductive layer is formed on both of the substrates constituting the liquid crystal display element, a voltage is applied between the two conductive layers, and the liquid crystal material sandwiched therebetween changes the alignment state according to the voltage. Display. Therefore, the structure described above can be formed in any desired shape and form inside any conductive layer (between the conductive layer and the liquid crystal layer).

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples at all. In the examples, “parts” and “%” indicate “parts by mass” and “% by mass”, respectively.

<Particle size, particle size, number average particle size>
In each of the following Examples and Comparative Examples, the “shape” of the particle was determined by observing an electron micrograph of the particle. Also, the diameter when the electron micrograph image of the particles is a circle of the same area is defined as “particle diameter”, the particle diameter is determined for a large number of particles, and the average value of these 100 particles is referred to as “number average particle diameter”. did.

<Film thickness>
In each of the following examples and comparative examples, the film thickness was measured using a surface roughness meter P-10 (manufactured by TENCOR).

<Optical density>
In each of the following Examples and Comparative Examples, “optical density (OD)” is first described. Using the material for forming the liquid crystal alignment control protrusion of the present invention, a layer having the same thickness as that of the liquid crystal alignment control protrusion formation of the present invention is formed on the transparent substrate, and the pattern of the present invention is not exposed. A sample (film shape) for measurement was produced through the same process as the protrusion for controlling liquid crystal alignment. The transmission optical density of the sample was measured at 555 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100) to obtain (OD), and the transmission optical density of the glass substrate was separately measured by the same method. (OD ₀ ) was determined, and the value obtained by subtracting OD ₀ from OD was taken as the transmission optical density of the film.

<Chromaticity>
In each of the following examples and comparative examples, “chromaticity (ΔE)” is the same as that used for forming the liquid crystal alignment control protrusion of the present invention, and the liquid crystal alignment control protrusion of the present invention is formed on the transparent substrate. A sample for measurement is prepared through the same steps as the liquid crystal alignment control projection of the present invention except that a layer having the same thickness is formed and not exposed in a pattern, and the chromaticity of the sample is measured with a C light source. The deviation (ΔE) from the achromatic point (x = 0.333, y = 0.333) was determined.

<Preparation of metal fine particle dispersion>
Metal fine particle dispersions used in each Example and Comparative Example were prepared.

(Preparation of spherical silver dispersion)
The following compositions were mixed to prepare an aqueous solution.
〔composition〕
Silver 186 parts Distilled water 1000 parts Polyvinylpyrrolidone (ISP: PVP K-30) 80 parts Solsperse 20000 (Abisia Co., Ltd., dispersant) 12 parts

  While vigorously stirring the obtained aqueous solution, 31 parts of sodium borohydride was added and further stirred vigorously for 15 minutes to obtain silver fine particles. This liquid was centrifuged at 2000 rpm for 20 minutes to precipitate silver fine particles. After removing the supernatant, the excess salt was removed by washing with distilled water. The silver precipitate was then washed with acetone and dried. By mixing 60 parts of the obtained silver precipitate, 2.3 parts of Solsperse 20000 (manufactured by Avicia Co., Ltd., dispersant) and 247 parts of acetone, and irradiating with ultrasonic waves of 1000 W and 40 KHz for 10 minutes, A fine particle dispersion was obtained. When observed with an electron microscope, the number average particle diameter was 12 nm, which was a spherical particle.

(Preparation of spherical silver tin alloy fine particle dispersion)
The following compositions were mixed to prepare an aqueous solution.
〔composition〕
• Tin (II) chloride II hydrate (SnCl ₂ · 2H ₂ O) 45 parts • Potassium pyrophosphate (K ₄ P ₂ O ₇ ) 200 parts • Silver iodide (AgI) 5 parts • Silver iodide (KI) 330 parts ・ Distilled water 1500 parts ・ Solsperse 20000 (manufactured by Avicia Co., Ltd., dispersant) 2.3 parts ・ Polyvinylpyrrolidone (ISP: PVP K-30) 40 parts

  While vigorously stirring this aqueous solution, 16 parts of sodium borohydride was added and further stirred vigorously for 15 minutes to obtain silver tin alloy fine particles. This solution was centrifuged at 2000 rpm for 20 minutes to precipitate silver tin alloy fine particles. After removing the supernatant, the excess salt was removed by washing with distilled water. The silver tin alloy precipitate was then washed with acetone and dried. By mixing 50 parts of the obtained silver tin alloy precipitate, 1.5 parts of Solsperse 20000 (dispersant manufactured by Avicia Co., Ltd.) and 274 parts of acetone, and irradiating with ultrasonic waves of 1000 W and 40 KHz for 5 minutes, A silver tin alloy fine particle dispersion was obtained. When observed with an electron microscope, the number average particle diameter was 26 nm, which was a spherical particle.

(Preparation of spherical silver sulfide fine particle dispersion)
95 parts of silver acetate was dissolved in 900 parts of diethylaminoethanol (DEAE). While vigorously stirring at 40 ° C., 280 parts of a 20% aqueous sodium sulfide solution was added. The mixture was stirred at 40 ° C. for 30 minutes, and the whole amount was filtered. After washing the filtrate with distilled water and DEAE, 3.2 parts of Solsperse 24000GR (dispersant manufactured by Avicia Co., Ltd.) and 414 parts of ethyl methyl ketone were mixed and irradiated with 1000 W, 40 KHz ultrasonic waves for 10 minutes to form a spherical shape. A silver sulfide fine particle dispersion was obtained. When observed with an electron microscope, the number average particle diameter was 30 nm, which was a spherical particle.

(Preparation of spherical silver / silver sulfide composite fine particle dispersion)
While stirring 5000 parts of spherical silver fine particle dispersion prepared in accordance with the method described in the above item <Preparation of spherical silver fine particle dispersion> at 40 ° C., 196 parts of 5.0% sodium sulfide aqueous solution was added, and further 1 hour. Stir.
5000 parts of the silver / silver sulfide composite fine particle dispersion obtained as described above was subjected to circular centrifugation at 2000 rpm for 5 minutes to precipitate the silver / silver sulfide composite fine particles. After removing the supernatant, it was washed with distilled water to remove unnecessary salts.
Next, the silver / silver sulfide composite fine particle precipitate is washed with methyl alcohol and dried to obtain an aggregate. This aggregate 64 parts, Solspers 20000 (Avicia Co., Ltd., dispersant), methyl ethyl ketone 264 The parts were mixed. This was irradiated with ultrasonic waves of 1000 W and 40 KHz for 10 minutes to obtain a spherical silver / silver sulfide composite fine particle dispersion. When observed with an electron microscope, the number average particle diameter was 21 nm, which was a spherical particle.

(Preparation of shape anisotropic silver fine particle dispersion)
To 112 parts of gelatin, 3,488 parts of distilled water was added and the resulting mixture was heated to about 47 ° C. to dissolve the gelatin. To this, 4.0 parts of calcium acetate and 2.0 parts of potassium borohydride were added. Immediately thereafter, 6.0 parts of silver nitrate dissolved in 1000 parts of distilled water was added with rapid stirring. Distilled water was added to adjust the final mass to 5000 parts.
The product was then cooled to near the gelation temperature and passed through a small hole into the cooled water, thereby forming a very fine noodle (linear slurry). In order to prevent noodles from forming a molten mass, the noodles were diluted with water to prepare a noodle slurry of water 1 to noodle 3.
To 650 parts of the noodle slurry, 6.5 parts of potassium hydroquinone monosulfonate dissolved in 81 parts of distilled water and 0.3 part of KCl were added. The noodle slurry was cooled to about 6 ° C. Moreover, the following two types of solutions A and B were produced in separate containers.
[Solution A]
Sodium sulfite (anhydrous) 19.5 parts Sodium bisulfite (anhydrous) 0.98 parts Distilled water 122.0 parts [Solution B]
・ Silver nitrate 9.75 parts ・ Distilled water 122.0 parts

  The solutions A and B were mixed to form a white precipitate that disappeared when stirring was continued. This mixture was then immediately added to the noodle slurry with rapid stirring in a short time (within 5 minutes). The temperature was maintained at 10 ° C. and the reaction was allowed to proceed for about 80 minutes until all the soluble silver salt was reduced onto the nuclei. The resulting blue slurry particulates were passed through the slurry in a nylon mesh bag through the slurry and washed for about 30 minutes with wash water passing through the bag to wash away all the salt.

The blue silver dispersed and washed in the gel slurry is dehydrated and silver dispersed until the mass of the product is 412 parts so that a blue silver dispersion having 1.5% by weight silver is obtained when melted. A slurry was prepared.
To 5000 g of the silver dispersion slurry obtained as described above, 25 g of a dispersant (Lapisol B-90, manufactured by Nippon Oil & Fats Co., Ltd.) and 1000 g of a 5% by weight papain aqueous solution were added and stirred at 37 ° C. for 24 hours.

This solution was centrifuged at 2000 rpm for 5 minutes to precipitate silver fine particles. Thereafter, the supernatant was removed, and then washed with distilled water to remove the gelatin degradation product decomposed by the enzyme.
Next, the silver fine particle sediment was washed with methyl alcohol and dried to obtain an aggregate of about 85 g of silver fine particles. 73.5 g of this aggregate, 1.05 g of Solsperse 20000 (dispersant manufactured by Avicia Co., Ltd.) and 264 g of methyl ethyl ketone were mixed. This was dispersed with an Eiger mill for 2 hours to obtain a shape anisotropic silver fine particle dispersion. When the shape anisotropic silver fine particle dispersion was observed with an electron microscope, the number average particle diameter was 37 nm and it was a plate-like fine particle (shape anisotropic fine particle).
The Eiger mill dispersion was performed using “Eiger Mill M-50 type” (media: 0.6 mm diameter zirconia beads, 70% bead filling rate) manufactured by Eiger Japan. The same applies to the following Eiger mill dispersion.

<Preparation of pigment dispersion>
The following pigment dispersions used in each example and comparative example were prepared.

(Preparation of pigment dispersion (I))
The following composition was mixed to prepare a pigment dispersion (I).
-Composition-
-151 parts of the above-mentioned shape anisotropic silver fine particle dispersion-128 parts of the following yellow pigment dispersion

(Preparation of pigment dispersion (b))
The following composition was mixed to prepare a pigment dispersion (b).
-Composition-
-101 parts of the above-mentioned shape anisotropic silver fine particle dispersion-128 parts of the following K pigment dispersion 1

(Preparation of pigment dispersion (c))
The following composition was mixed to prepare a pigment dispersion (C).
-Composition-
-303 parts of the above spherical silver fine particle dispersion-407 parts of the following blue pigment dispersion-179 parts of the following red pigment dispersion

(Preparation of pigment dispersion (d))
The following composition was mixed to prepare a pigment dispersion (d).
-Composition-
-432 parts of the above spherical silver fine particle dispersion-475 parts of the following blue pigment dispersion

(Preparation of pigment dispersion (e))
The following composition was mixed to prepare a pigment dispersion (e).
-Composition-
-297 parts of the above spherical silver tin alloy fine particle dispersion-187 parts of the following blue pigment dispersion

(Preparation of pigment dispersion (f))
The following composition was mixed to prepare a pigment dispersion (f).
-Composition-
-308 parts of the above spherical silver sulfide fine particle dispersion-174 parts of the following blue pigment dispersion

(Preparation of pigment dispersion (g))
The following composition was mixed to prepare a pigment dispersion (g).
-Composition-
-198 parts of the above spherical silver / silver sulfide composite fine particle dispersion-91 parts of the following blue pigment dispersion

The compositions of the yellow pigment dispersion, blue pigment dispersion and red pigment dispersion are shown below. The composition of the K pigment dispersion 1 will be described later.
-Composition of yellow pigment dispersion-
・ C. I. Pigment Yellow 185 8 parts Polymer 7.6 parts (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000)
Propylene glycol monomethyl ether acetate 82.4 parts

-Composition of blue pigment dispersion-
・ C. I. Pigment Blue 15: 6 10 parts Polymer 12.5 parts (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000)
N, N′-bis- (3-diethylaminopropyl) -5- {4- [2-oxo-1- (2-oxo-2,3-dihydro-1H-benzimidazol-5-ylcarbamoyl) -propylazo ] -Benzoylamino} -isophthalamide
0.63 parts ・ Propylene glycol monomethyl ether acetate 76.9 parts

-Composition of red pigment dispersion-
・ C. I. Pigment Red 254 8 parts Polymer 6.4 parts (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000)
N, N′-bis- (3-diethylaminopropyl) -5- {4- [2-oxo-1- (2-oxo-2,3-dihydro-1H-benzimidazol-5-ylcarbamoyl) -propylazo ] -Benzoylamino} -isophthalamide
0.8 part ・ 84.8 parts of propylene glycol monomethyl ether acetate

[Example 1]
<Production of liquid crystal display device>
<Production of resin transfer material>
On a polyethylene terephthalate film temporary support having a thickness of 75 μm, a coating solution CU1 for a thermoplastic resin layer having the following formulation CU1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution PC1 having the following formulation PC1 was applied and dried. Furthermore, a colored photosensitive resin composition K1 having the composition shown in Table 1 below was applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm on the temporary support and a dry film thickness of 1 were applied. A 0.6 μm intermediate layer and a photosensitive resin layer having a dry film thickness of 2.4 μm were provided, and a protective film (12 μm thick polypropylene film) was further pressure-bonded from above the photosensitive resin layer.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer are integrated is prepared, and the sample name is the photosensitive resin transfer material. It was set as K1.

-Composition of coating liquid CU1 for thermoplastic resin layer (prescription CU1)-
The following composition was mixed to obtain a coating liquid CU1 for a thermoplastic resin layer.
・ Methanol 11.1 parts ・ Propylene glycol monomethyl ether acetate 6.36 parts ・ Methyl ethyl ketone 52.4 parts ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 5.83 parts (copolymerization composition ratio (mol) Ratio) = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 100,000, Tg≈70 ° C.)
Styrene / acrylic acid copolymer 13.6 parts (copolymerization composition ratio (molar ratio) = 65/35, weight average molecular weight = 10,000, Tg≈100 ° C.)
Compound obtained by dehydrating condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (Shin Nakamura Chemical Co., Ltd., 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane) 9.1 parts Surfactant 1 0.54 parts (manufactured by Dainippon Ink and Chemicals, trade name: MegaFuck F780F)

The composition of the surfactant 1 is as follows.
_{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2: and 40 _{parts, H (O (CH 3)} CHCH 2) 7 OCOCH = CH 2: and 55 _{parts, H (OCH 2 CH 2)} 7 OCOCH = CH 2 : 5 parts copolymer (weight average molecular weight 30,000) 30 parts methyl ethyl ketone 70 parts

-Composition of intermediate layer coating liquid PC1 (prescription PC1)-
The following composition was mixed to obtain an intermediate layer coating solution PC1.
〔composition〕
Polyvinyl alcohol 2.90 parts (saponification degree 82%, polymerization degree 500, manufactured by Kuraray Co., Ltd., PVA-405)
Polyvinylpyrrolidone (ISP, PVP K-30) 1.49 parts Polypropylene glycol 0.32 parts (Asahi Denka Co., Ltd., Adeka Polyether G-300)
・ Methanol 42.9 parts ・ Distilled water 52.4 parts

  Next, the colored photosensitive resin composition K1 used in the production of the black photosensitive resin transfer material K1 is changed to the following colored photosensitive resin compositions R1, G1, and B1 having the compositions shown in Table 1 below. Otherwise, photosensitive resin transfer materials R1, G1 and B1 were produced by the same method as described above.

(Formation of black (K) image)
The glass detergent solution prepared on the alkali-free glass substrate was washed with a rotating brush having nylon bristles while sprayed for 20 seconds by shower, and further washed with pure water. Thereafter, a silane coupling liquid (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and pure water The shower was washed. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After the protective film of the photosensitive resin transfer material K1 is peeled off, a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)) is used, and a substrate heated at 100 ° C. for 2 minutes, a rubber roller temperature of 130 ° C., Lamination was performed at a linear pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, in a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, the substrate and mask (quartz exposure mask with image pattern) are set up vertically. The distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

  Next, triethanolamine developer (30% by mass of triethanolamine, 0.1% by mass in total of polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate and stearyl ether, and the remaining pure water The stock solution prepared and stored in the composition was flattened at 30 ° C. for 50 seconds with a 12-fold dilution with pure water (a solution obtained by diluting 1 part by weight of the stock solution and 11 parts by weight of pure water) Shower development was performed at a nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film. Subsequently, after air was blown off on the upper surface of the substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

  Subsequently, Na carbonate-based developer (0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included Product name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa, and the photosensitive resin layer was developed to obtain a patterned pixel.

Continued use of detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1” (Fuji Photo Film Co., Ltd.) diluted 10 times with pure water. , Sprayed with a shower at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa, and further rubbed the image formed with a rotating brush having nylon bristles to obtain a black (K) image. Further, the substrate was post-exposed with light of 500 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp from the resin layer side, and then heat-treated at 220 ° C. for 15 minutes.

  The substrate on which this black (K) image was formed was washed again with a brush as described above, washed with pure water shower, and then heated at 100 ° C. for 2 minutes with a substrate preheating device without using a silane coupling solution. .

(Formation of red (R) pixels)
Using the photosensitive resin transfer material K1, a red (R) pixel was obtained on a substrate on which a black (K) image was formed, in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was performed at 35 ° C. for 35 seconds.
The photosensitive resin layer R1 has a thickness of 2.0 μm. I. Pigment red 254 and C.I. I. The application amounts of Pigment Red 177 were 0.88 g / m ² and 0.22 g / m ² , respectively.
The substrate on which the red (R) pixels are formed is washed again with a brush as described above, and then washed with a pure water shower. Then, without using a silane coupling solution, the substrate is preheated at 100 ° C. for 2 minutes. Heated.

(Formation of green (G) pixels)
Using the photosensitive resin transfer material G1, green (G) pixels were obtained on the substrate on which the red (R) pixels were formed, in the same process as the photosensitive resin transfer material R1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate-based developer was performed at 34 ° C. for 45 seconds.
The photosensitive resin layer G1 has a film thickness of 2.0 μm. I. Pigment green 36 and C.I. I. Each coating amount of Pigment Yellow 150, 1.12g / m ^2, was 0.48 g / m ^2.
The substrate on which the red (R) and green (G) images were formed was washed again with the brush as described above, and after pure water shower washing, without using a silane coupling solution, the substrate was preheated to 100 ° C. For 2 minutes.

(Formation of blue (B) pixels)
A blue (B) pixel is formed on a substrate on which the red (R) pixel and the green (G) pixel are formed using the photosensitive resin transfer material B1 in the same process as the photosensitive resin transfer material R1. Obtained. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate-based developer was performed at 36 ° C. for 40 seconds.
The photosensitive resin layer B1 has a thickness of 2.0 μm. I. Pigment blue 15: 6 and C.I. I. Each coating amount of Pigment Violet 23, 0.63g / m ^2, was 0.07 g / m ^2.

The substrate on which the R, G, B and K images were formed was baked at 240 ° C. for 50 minutes to obtain the desired color filter.
Further, a transparent electrode film was formed on the obtained color filter by sputtering of ITO.

  Here, preparation of the colored photosensitive resin compositions K1, R1, G1, and B1 described in Table 1 below will be described.

-Preparation of colored photosensitive resin composition K1-
The colored photosensitive resin composition K1 first measures K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, mixes at a temperature of 24 ° C. (± 2 ° C.), and stirs at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 1, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine, Hydroquinone monomethyl ether and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

In addition, the composition of K pigment dispersant, the binder 1, and DPHA liquid among the colored photosensitive compositions K1 of the said Table 1 is shown below.
[Composition of K pigment dispersion 1]
Carbon black (NIPX35, manufactured by Degussa) 13.1 partsN, N′-bis- (3-diethylaminopropyl) -5- {4- [2-oxo-1- (2-oxo-2,3- Dihydro-1H-benzimidazol-5-ylcarbamoyl) -propylazo] -benzoylamino} -isophthalamide
0.65 part / polymer 6.72 part (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000)
・ 79.53 parts of propylene glycol monomethyl ether acetate

[Composition of binder 1]
・ 27 parts of polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, weight average molecular weight 44,000)
・ Propylene glycol monomethyl ether acetate 73 parts

[Composition of DPHA solution]
・ 76 parts of dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ,
Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)
・ Propylene glycol monomethyl ether 24 parts

-Preparation of colored photosensitive resin composition R1-
First, the colored photosensitive resin composition R1 shown in Table 1 was obtained by measuring R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and measuring the temperature at 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes. Then, methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) in the amounts shown in Table 1 -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine and phenothiazine were weighed and added in this order at a temperature of 24 ° C. (± 2 ° C.). Stir for minutes. Furthermore, ED152 (phosphate ester special activator, manufactured by Enomoto Kasei Co., Ltd., “HIPLAAD ED152”) in the amount shown in Table 1 was weighed, added at a temperature of 24 ° C. (± 2 ° C.), and stirred at 30 rpm for 30 minutes. Further, the surfactant 1 in the amount shown in Table 1 was weighed, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 30 minutes, and then filtered through a nylon mesh # 200.

The compositions of R pigment dispersion 1, R pigment dispersion 2 and binder 2 in Table 1 are shown below.
[Composition of R Pigment Dispersion 1]
・ C. I. Pigment Red 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 8 parts N, N′-bis- (3-diethylaminopropyl) -5- {4- [2-oxo -1- (2-oxo-2,3-dihydro-1H-benzimidazol-5-ylcarbamoyl) -propylazo] -benzoylamino} -isophthalamide
0.8 parts / polymer 8 parts (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000)
Propylene glycol monomethyl ether acetate 83.2 parts

[Composition of R Pigment Dispersion 2]
・ C. I. Pigment Red 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) 18 parts / polymer 12 parts (random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 3 .70,000)
・ 70 parts of propylene glycol monomethyl ether acetate

[Composition of binder 2]
-27 parts of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, weight average molecular weight 30,000)
・ Propylene glycol monomethyl ether acetate 73 parts

  The composition was dispersed at a peripheral speed of 9 m / s using a motor mill “M-50” (manufactured by Eiger Japan) and zirconia beads having a diameter of 0.5 mm to prepare a pigment dispersion.

-Preparation of colored photosensitive resin composition G1-
The colored photosensitive resin composition G1 shown in Table 1 first measures the amount of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1, and the temperature is 24 ° C. ( (± 2 ° C.) and stirred at 150 rpm for 10 minutes. Next, methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, 2,4-bis (2, 4- ( Trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and phenothiazine were weighed and added in this order at a temperature of 24 ° C. (± 2 ° C.). And stirred at 150 rpm for 30 minutes. Further, the amount of the surfactant 1 described in Table 1 above was measured, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200 to give a colored photosensitive resin composition. G1 was obtained.

The compositions of G pigment dispersion 1 and Y pigment dispersion 1 in Table 1 are shown below.
-G pigment dispersion 1 ("trade name: GT-2" manufactured by FUJIFILM Electronics Materials Co., Ltd.)

・ Y pigment dispersion 1 (manufactured by Mikuni Color Co., Ltd., trade name: CF Yellow EX3393)

-Preparation of colored photosensitive resin composition B1-
The colored photosensitive resin composition B1 shown in Table 1 first measures B pigment dispersion 1, B pigment dispersion 2 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 above, at a temperature of 24 ° C. The mixture was mixed at (± 2 ° C.) and stirred at 150 rpm for 10 minutes. Subsequently, methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4-oxadiazole, and phenothiazine in the amounts shown in Table 1 were weighed out and the temperature was 25 ° C. (± 2 ° C.) were added in this order, and the mixture was stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. Further, the amount of the surfactant 1 described in Table 1 above was measured, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 5 minutes, and filtered through a nylon mesh # 200 to give a colored photosensitive resin composition. B1 was obtained.

  The compositions of B pigment dispersion 1, B pigment dispersion 2 and binder 3 in Table 1 are shown below.

-B pigment dispersion 1 (made by Mikuni Color Co., Ltd., trade name: CF Blue EX3357)
-B pigment dispersion 2 (made by Mikuni Color Co., Ltd., trade name: CF Blue EX3383)

[Composition of binder 3]
・ 27 parts of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, weight average molecular weight 30,000)
・ Propylene glycol monomethyl ether acetate 73 parts

<Preparation of photosensitive transfer material for liquid crystal alignment control projection>
A thermoplastic resin layer coating liquid CU1 comprising the above-mentioned formulation CU1 was applied on a 75 μm thick polyethylene terephthalate film temporary support and dried to provide a thermoplastic resin layer having a dry film thickness of 15 μm.
Next, the intermediate layer coating liquid PC1 made of the prescription PC1 was applied onto the thermoplastic resin layer and dried to provide an intermediate layer having a dry film thickness of 1.6 μm.
On the intermediate layer, a liquid crystal alignment control projection photosensitive resin layer coating liquid T1 having the following formulation T1 is applied and dried, and a liquid crystal alignment control projection photosensitive resin layer having a dry film thickness of 2.0 μm is formed. Provided.

-Composition (Prescription T1) of coating liquid T1 for photosensitive resin layer for protrusions for controlling liquid crystal alignment
Benzyl methacrylate / methacrylic acid copolymer 37.9 parts (molar ratio = 73/27 weight average molecular weight 30000)
Dipentaerythritol hexaacrylate 29.1 parts Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 1.7 parts 570.6 parts of the above pigment dispersion (I) 560 parts of propylene glycol monomethyl ether acetate 280 parts of methyl ethyl ketone. 0.04 part of the surfactant 1

  Further, a 12 μm-thick polypropylene film is attached as a cover film on the surface of the liquid crystal alignment control projection photosensitive resin layer, and the thermoplastic resin layer, the intermediate layer, and the liquid crystal alignment control projection for the temporary support. A transfer material in which a photosensitive resin layer and a cover film were laminated in this order was produced.

(Formation of liquid crystal alignment control protrusions)
The cover film is peeled off from the liquid crystal alignment control protrusion transfer material obtained above, and the surface of the photosensitive resin layer and the surface of the color filter side substrate on which the ITO film is provided are overlapped to form a laminator (Co., Ltd.). ) Using Hitachi Industries, Ltd. (Lamic II type)) under the conditions of a linear pressure of 100 N / cm, a temperature of 130 ° C., and a conveying speed of 2.2 m / min. Thereafter, only the temporary support of the transfer material was peeled and removed at the interface with the thermoplastic resin layer. In this state, the photosensitive resin layer, the intermediate layer, and the thermoplastic resin layer are laminated in this order on the color filter side substrate.
Next, a proximity exposure machine is arranged above the outermost thermoplastic resin layer so that the photomask is at a distance of 100 μm from the surface of the thermoplastic resin layer, and an ultrahigh pressure mercury lamp is passed through the photomask. Proximity exposure was performed at an irradiation energy of 100 mJ / cm ² . Thereafter, a triethanolamine aqueous solution similar to that used for the black (K) image formation was sprayed onto the substrate at 30 ° C. for 30 seconds using a shower type developing device to dissolve and remove the thermoplastic resin layer and the intermediate layer. . At this stage, the photosensitive resin layer was not substantially developed.

  Subsequently, using the same sodium carbonate developer as that used for the black (K) image formation, shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer to obtain a patterned pixel. It was.

  Subsequently, using the same cleaning agent as that used for the black (K) image formation, the residue was removed with a rotating brush having a shower and nylon bristles at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Then, a liquid crystal alignment control protrusion made of a photosensitive resin layer patterned into a desired shape was formed on the color filter side substrate. Then, the color filter side substrate on which the liquid crystal alignment control protrusions were formed was baked at 240 ° C. for 50 minutes, whereby black liquid crystal alignment control protrusions could be formed on the color filter side substrate. The shape of the projection for controlling the alignment of black liquid crystal was observed by a scanning electron microscope, and as a result, had a saddle-shaped cross-sectional shape with a line width of 14.1 μm and a center height of about 1.5 μm.

  Further, a liquid crystal display element was produced by combining the drive side substrate and the liquid crystal material with the color filter side substrate obtained above. That is, a TFT substrate on which TFTs and pixel electrodes (conductive layers) are arrayed is prepared as a driving side substrate, the surface of the TFT substrate on which the pixel electrodes and the like are provided, and the color filter obtained from the above. The side substrate was disposed so as to face the surface on which the black liquid crystal alignment control protrusions were formed, and a spacer material was placed and fixed with a gap. By enclosing a liquid crystal material in the gap and providing a liquid crystal layer for image display, a 20-inch liquid crystal display device of the present invention having a liquid crystal alignment control protrusion between the conductive layer and the substrate was produced. The following display performance was evaluated. The following results are shown in Table 2.

[Evaluation]
<Contrast>
The difference between the brightness when the liquid crystal display devices manufactured in the above Examples and Comparative Examples were displayed in black and the brightness when displayed in white was measured, and the results are shown in Table 2 below.
For the measurement of black and white contrast, “BM-5” manufactured by TOPCON CORPORATION JAPAN was used as a luminance meter, and this was measured by setting the measurement angle to 2 ° at a distance of 50 cm in the vertical direction from the panel surface. . The measurement was performed in a dark room.

<Mura>
First, a gray test signal was inputted to the liquid crystal display device, and the presence or absence of unevenness was determined by visual observation and observation with a magnifying glass. “5” indicates that no unevenness is observed visually or with a loupe, “4” indicates that unevenness is observed only with the loupe, and “3” indicates that unevenness is slightly observed visually. Was recognized as “2”, and visually noticeable unevenness was defined as “1”.

<Comprehensive evaluation>
Display performance evaluation of the display device determined from the above evaluation items. Compared to the past, “◎” indicates that it is judged to be particularly superior, “○” indicates that it is determined to be superior, and “○ △” indicates that it is considered slightly superior. What was judged was “△”, and those that were completely inferior or that were judged to be equal to or less than the conventional one were marked “X”.

[Example 2]
In Example 1, except that the addition amount of the pigment dispersion (A) in the formulation T1 was changed to 272.6 parts, and the irradiation energy of the proximity exposure by the ultrahigh pressure mercury lamp was changed to 50 mJ / cm ^2. A liquid crystal display device was produced in the same manner as in Example 1. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 3]
A color filter was produced in the same manner as in Example 1, and a transparent electrode film was formed thereon by sputtering ITO.

(Formation of liquid crystal alignment control protrusions)
In Example 1, the coating liquid for the photosensitive black resin layer for liquid crystal alignment control protrusions, in which the addition amount of the pigment dispersion liquid (a) in the formulation T1 was changed to 141.1 parts, was applied to the color filter substrate by a slit coater. It was applied on ITO and dried.
Next, an intermediate layer having a dry film thickness of 1.6 μm was provided on the photosensitive black resin layer for liquid crystal alignment control protrusions using the intermediate layer coating liquid of the prescription PC1.
Next, a proximity exposure machine is arranged so that a photomask with a mask width of 14 μm is at a distance of 100 μm from the surface of the photosensitive resin layer, and an irradiation energy of 40 mJ / cm ² is applied by an ultrahigh pressure mercury lamp through the photomask. Proximity exposure. Thereafter, a KOH aqueous solution (KOH, containing a nonionic surfactant, trade name: CDK-1, manufactured by FUJIFILM Electromaterials Co., Ltd.) is sprayed onto a substrate at 30 ° C. for 40 seconds in a shower type developing device, and a photosensitive resin layer Unnecessary portions were removed by development. Then, a liquid crystal alignment control protrusion made of a photosensitive resin layer patterned into a desired shape was formed on the color filter side substrate. Next, the color filter side substrate on which the structure was formed was baked at 240 ° C. for 50 minutes, whereby liquid crystal alignment control protrusions could be formed on the color filter side substrate. Further, a liquid crystal display device was produced in the same manner as in Example 1. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 4]
In Example 1, the amount of addition of the pigment dispersion (I) in the formulation T1 was changed to 75.5 parts, and the irradiation energy of proximity exposure with an ultrahigh pressure mercury lamp was changed to 40 mJ / cm ^2. In the same manner, a liquid crystal display device was produced. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 5]
In Example 1, the amount of addition of the pigment dispersion liquid (A) in the formulation T1 was changed to 55.52 parts, and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was changed to 40 mJ / cm ^2. In the same manner, a liquid crystal display device was produced. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

Example 6
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 214.8 parts of the pigment dispersion (B), and the irradiation energy of the proximity exposure by the ultrahigh pressure mercury lamp was 40 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 7]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 116.4 parts of the pigment dispersion (B), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 40 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 8]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 74.0 parts of the pigment dispersion (B), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 40 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 9]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 39.1 parts of the pigment dispersion (B), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 40 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that the change was made to 2. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 10]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 were changed to 828.8 parts of the pigment dispersion (C), and the irradiation energy of the proximity exposure using an ultrahigh pressure mercury lamp was set to 60 mJ / cm ² . A liquid crystal display device was produced in the same manner as in Example 1 except for the change. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 11]
<Production of liquid crystal display device>
<Preparation of color filter>
-Formation of black (K) image-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
The substrate is cooled and temperature-controlled at 23 ° C., and then colored as described in Table 1 above with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Photosensitive resin composition K1 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2.4 μm. The photosensitive resin layer K1 was obtained.
In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the exposure mask surface and the photosensitive film are exposed in a state where the substrate and the mask (quartz exposure mask having an image pattern) are vertically set up. The distance between the conductive resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .

  Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji) The film was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

-Formation of red (R) image-
Using the colored photosensitive resin composition R2 having the composition shown in Table 1 on the substrate on which the black (K) image was formed, heat-treated red ( R) An image was formed.

-Green (G) image formation-
Using the colored photosensitive resin composition G2 having the composition shown in Table 1 on the substrate on which the black (K) and red (R) images are formed, the same process as the formation of the black (K) image Thus, a heat-treated green (G) image was formed.

-Formation of blue (B) image-
Formation of the black (K) image using the colored photosensitive resin composition B2 having the composition shown in Table 1 on a substrate on which the black (K), red (R), and green (G) images were formed. In the same process as above, a heat-treated blue (B) image was formed to obtain the target color filter.

In addition, the preparation methods of colored photosensitive resin composition R2, G2, and B2 are based on the preparation method of said colored photosensitive resin composition R1, G1, and B1, respectively.
Further, a transparent electrode film was formed on the obtained color filter by sputtering of ITO.

<Preparation of liquid crystal alignment control projection>
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 519.5 parts of the pigment dispersion (C), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 50 mJ / cm ^2. A liquid crystal display device was produced in the same manner as in Example 1 except that the color filter was used. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 12]
First, a color filter was formed in the same manner as in Example 11.
Next, in Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 212.0 parts of the pigment dispersion (C). Application for photosensitive black resin layer for protrusions for liquid crystal alignment control The liquid was applied onto the ITO of the color filter substrate with a slit coater and dried. Further, a liquid crystal display device was produced in the same manner as in Example 3 except that the irradiation energy of the proximity exposure with an ultrahigh pressure mercury lamp was changed to 40 mJ / cm ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 13]
In Example 1, 570.6 parts of the pigment dispersion liquid (A) in the formulation T1 was changed to 462.1 parts of the pigment dispersion liquid (D), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 50 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 14]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to the above-mentioned pigment dispersion (D) 152.9, and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 50 mJ / cm ^2. A liquid crystal display device was produced in the same manner as in Example 1 except that the above was changed. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 15]
In Example 1, 570.6 parts of the pigment dispersion liquid (A) in the formulation T1 was changed to 254.7 parts of the pigment dispersion liquid (E), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 50 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 16]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 123.0 parts of the pigment dispersion (E), and the irradiation energy of the proximity exposure with an ultrahigh pressure mercury lamp was 50 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 17]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 77.4 parts of the pigment dispersion (E), and the irradiation energy of the proximity exposure with an ultrahigh pressure mercury lamp was 40 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 18]
First, a color filter was formed in the same manner as in Example 11.
Next, in Example 1, for the photosensitive black resin layer for protrusions for controlling liquid crystal alignment, 570.6 parts of the pigment dispersion (A) in the formulation T1 were changed to 413.2 parts of the pigment dispersion (F). The coating solution was applied onto the ITO of the color filter substrate with a slit coater and dried.
Further, a liquid crystal display device was produced in the same manner as in Example 3 except that the irradiation energy of the proximity exposure using an ultrahigh pressure mercury lamp was changed to 60 mJ / cm ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 19]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 303.5 parts of the pigment dispersion (F), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 50 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that it was changed to ² . The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 20]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 213.0 parts of the pigment dispersion (F), and the irradiation energy of the proximity exposure with an ultrahigh pressure mercury lamp was 50 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that the change was made to 2. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 21]
In Example 1, 570.6 parts of the pigment dispersion (I) in the formulation T1 was changed to 114.4 parts of the pigment dispersion (F), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was set to 40 mJ / cm ² . A liquid crystal display device was produced in the same manner as in Example 1 except for the change. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 22]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was 544.4 parts of the pigment dispersion (G), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 60 mJ / cm ² . A liquid crystal display device was produced in the same manner as in Example 1 except for the change. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 23]
In Example 1, 570.6 parts of the pigment dispersion (I) in the formulation T1 was changed to 281.0 parts of the pigment dispersion (G), and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was 60 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that the change was made to 2. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

[Example 24]
In Example 1, the prescription T1 was changed to the following prescription T2, the irradiation energy of the proximity exposure by the ultrahigh pressure mercury lamp was changed to 150 mJ / cm ² , the development method was changed to the following method, and further as follows: A liquid crystal display device was produced in the same manner as in Example 1 except that the liquid crystal alignment control protrusions were polished. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

<Composition of coating liquid T2 for photosensitive resin layer for protrusions for controlling liquid crystal alignment (prescription T2)>
-Cresol novolak resin A (m / p = 60/40, MW = 2600) 19 parts- Cresol novolak resin B (m / p = 80/20, MW = 2200) 19 parts ("m / p" is cresol novolak resin (Indicates the molar ratio of meta-position / para-position in the middle, and “MW” represents the weight average molecular weight.)
4'-t-octylphenyl naphthoquinone diazide-5-sulfonate 12 parts, pigment dispersion (g) 97.4 parts propylene glycol monomethyl ether acetate 560 parts methyl ethyl ketone 280 parts, surfactant 1 0.04 parts (Dainippon Ink Chemical Co., Ltd., trade name: MegaFuck F780F)

-Development method-
Triethanolamine-based developer (30% by mass of triethanolamine, 0.1% by mass of polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate and stearyl ether, formulated with the composition of the remaining pure water The stored stock solution was diluted 12 times with pure water (a solution obtained by diluting the stock solution with 1 part by mass and 11 parts by mass of pure water) at 30 ° C. for 50 seconds, with a flat nozzle pressure. Shower development was performed at 0.04 MPa to remove the thermoplastic resin layer and the oxygen barrier film.
Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was developed while spraying on the substrate at 33 ° C. for 30 seconds with a shower type developing device, and unnecessary portions of the photosensitive resin layer were developed and removed, and the liquid crystal alignment control protrusions Got a pattern.

-Polishing-
A polishing liquid in which a polyurethane foam cloth having a JIS hardness of 85 is applied as a polishing pad to a plate of a flat plate polishing machine, and an alumina abrasive of primary particles 0.1 to 1.0 μm (secondary particles 30 to 80 μm) is dispersed as a polishing liquid. The polishing liquid was dropped onto a polishing pad, and polishing was performed with the surface of the color filter substrate on which the protrusions for controlling liquid crystal alignment were formed facing each other. The polishing pressure was 1.5 × 10 ⁴ Pa, the number of rotations was 30 rpm, and the vertical cross-sectional shape of the liquid crystal alignment control protrusion was formed like a bowl.

[Example 25]
In Example 1, except that the addition amount of the pigment dispersion (A) in the formulation T1 was changed to 618.9 parts, and the irradiation energy of the proximity exposure by the ultrahigh pressure mercury lamp was changed to 80 mJ / cm ^2. In the same manner, a liquid crystal display device was produced. The “flicker” of the obtained liquid crystal display device and the “relative permittivity” of the liquid crystal alignment control protrusion were evaluated as follows. The results are shown in Table 3 below.

[ Reference Example 26]
In Example 1, the amount of addition of the pigment dispersion (A) in the formulation T1 was changed to 47.7 parts, and the irradiation energy of proximity exposure using an ultrahigh pressure mercury lamp was changed to 40 mJ / cm ^2. In the same manner, a liquid crystal display device was produced. The “flicker” of the obtained liquid crystal display device and the “relative permittivity” of the liquid crystal alignment control protrusion were evaluated as follows. The results are shown in Table 3 below.

<Relative permittivity>
For “relative dielectric constant”, first, using the material for forming the liquid crystal alignment control protrusion of the present invention, on the ITO vapor deposition substrate, a layer having the same thickness as that of the liquid crystal alignment control protrusion formation of the present invention is formed, A sample for measurement (film shape) was prepared through the same steps as the liquid crystal alignment control protrusion of the present invention except that the pattern was not exposed. And the capacitor | condenser was formed by vapor-depositing gold to the predetermined area of a sample, the electrostatic capacitance was measured, and the dielectric constant ((epsilon)) was computed.

<With flicker>
When a gray test signal was input to the liquid crystal display device, it was observed visually and with a magnifying glass to determine the degree of flickering.

[Comparative Example 1]
In Example 1, the prescription T1 is changed to the following prescription T3, the irradiation energy of the proximity exposure with an ultrahigh pressure mercury lamp is changed to 150 mJ / cm ² , and development is performed in the same manner as in Example 24, for controlling the liquid crystal alignment A liquid crystal display device was produced in the same manner as in Example 1 except that the protrusions were polished. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1.

<Composition of Coating Liquid T3 for Photosensitive Resin Layer for Protrusion for Controlling Liquid Crystal Orientation (Prescription T3)>
Propylene glycol monomethyl ether acetate 600 parts Cresol novolak resin A (m / p = 60/40, MW = 2600) 30 parts Cresol novolak resin B (m / p = 80/20, MW = 2200) 30 parts (" “m / p” indicates the molar ratio of meta-position / para-position in the cresol novolak resin, and “MW” indicates the weight average molecular weight.)
-18 parts of 4'-t-octylphenyl naphthoquinone diazide-5-sulfonate-2.0 parts of 5% methanol solution of Victoria Pure Blue-0.05 part of the surfactant (Dainippon Ink Chemical Co., Ltd., trade name: MegaFuck F780F)

[Comparative Example 2]
In Example 1, 570.6 parts of the pigment dispersion (A) in the formulation T1 was changed to 347.6 parts of the spherical silver fine particle dispersion, and the irradiation energy of the proximity exposure by the ultrahigh pressure mercury lamp was 110 mJ / cm. ^A liquid crystal display device was produced in the same manner as in Example 1 except that the change was made to 2. The display performance of the obtained liquid crystal display device was evaluated in the same manner as in Example 1. In the liquid crystal display device of Comparative Example 5, the screen was colored yellow.

As can be seen from Table 2, the liquid crystal display device using the liquid crystal alignment control protrusion of the present invention was excellent in contrast and suppressed the occurrence of unevenness. In contrast, the liquid crystal display device of the comparative example has low contrast, unevenness, and poor overall evaluation.
Further, as can be seen from Table 3, it was found that when the relative dielectric constant (ε) increases, flickering occurs with the increase width.

It is the schematic for demonstrating the slope part of the processus | protrusion for liquid crystal orientation control. It is explanatory drawing for demonstrating the vertical cross-sectional shape of a bowl. It is a SEM image of the protrusion for liquid crystal orientation control which has a bowl-like longitudinal cross-sectional shape. It is a schematic sectional drawing for demonstrating the protrusion for liquid crystal orientation control of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal alignment control protrusion 2, 3, 6 Electrode 4 Liquid crystal layer 5 Liquid crystal molecule

Claims (14)

A protrusion for controlling the alignment of liquid crystal molecules used for controlling the alignment of liquid crystal molecules, the deviation of the chromaticity from the achromatic point (x = 0.333, y = 0.333) is within 30 within ΔE, and a metal Fine particles and a colorant ,
The metal fine particles have a number average particle size of 10 to 150 nm,
The metal forming the metal fine particles contains at least one of silver, gold, tin, nickel, platinum, and cobalt,
The metal fine particle content in the protrusion for controlling liquid crystal alignment is 0.5 to 9.0% by volume,
A protrusion for controlling liquid crystal alignment , wherein the relative dielectric constant is 2.0 to 6.0 .   2. The liquid crystal alignment control according to claim 1, wherein the metal fine particles are at least one selected from metal fine particles, alloy fine particles, metal compound fine particles, and composite fine particles of a metal and a metal compound. Protrusion.   3. The liquid crystal alignment control protrusion according to claim 1, wherein the colorant is carbon black and / or a pigment other than carbon black.   4. The liquid crystal according to claim 1, wherein a mass ratio (x / y) between the metal fine particles (x) and the colorant (y) is 0.1 to 10. 5. Projection for orientation control.   The projection for controlling liquid crystal alignment according to any one of claims 1 to 4, wherein the optical density is 0.3 or more and 10 or less. The metals particles, protrusions for controlling liquid crystal orientation according to any one of claims 1 to 5, wherein the silver particles. The liquid crystal alignment control protrusion according to any one of claims 1 to 6, wherein the cross-sectional shape is a ridge-like shape. A composition for use in making the protrusions for controlling liquid crystal orientation according to any one of claims 1 to 7, at least, (A) metals particles, (B) a colorant, (C) an alkali-soluble resin (D) A polymerizable monomer and (E) a photopolymerization initiator or a photopolymerization initiator system. A resin transfer material having at least one resin layer on a temporary support, wherein the resin layer contains the composition according to claim 8 . A method for producing a projection for controlling liquid crystal alignment, comprising a step of attaching the resin transfer material according to claim 9 to a substrate by a laminator. The manufacturing method of the processus | protrusion for liquid crystal orientation control characterized by including the process of apply | coating the composition of Claim 8 with a slit-shaped nozzle. The liquid crystal display device substrate, characterized by having a projection for controlling a liquid crystal alignment according to any one of claims 1-7. A liquid crystal display element comprising the substrate for a liquid crystal display device according to claim 12 . A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 12 .