JP5262926B2 - Manufacturing method of retardation substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transflective liquid crystal display device that is efficiently manufactured by a simplified method and has superior display performance. <P>SOLUTION: A retardation film includes a light-transmissive plane (20) and a solidified liquid crystal layer (230) which is supported on the plane body and is formed as a continuous film made of the same material. The solidified liquid crystal layer includes an anisotropic phase part (230R) having refractive index anisotropy and an isotropic phase part (230T) not having refractive index anisotropy, and a boundary (230H)between the anisotropic phase part and the isotropic phase part has a width of &lt;8 &mu;m. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an optical technique applicable to a transflective liquid crystal display device.

  Liquid crystal display devices are evaluated for space saving, light weight, and power saving because they are thin, and recently they are rapidly spreading to portable devices and television applications. The liquid crystal display device can perform multicolor display by providing a color filter substrate in the panel structure, and generally performs RGB three-color display or six-color display in which RBG pixels for reflection are added thereto. Is.

  In particular, a liquid crystal display device for portable devices may employ a reflective type or a transflective type liquid crystal display device in which a reflective part is partially formed in order to ensure visibility even under strong outdoor light in the daytime. Many. In such a case, in order to effectively utilize the reflected light, a λ / 4 retardation film, a λ / 2 retardation film, or the like is incorporated in the liquid crystal panel configuration as a member that forms part of the absorption-type circularly polarizing plate. .

  Usually, in a transflective liquid crystal display device, a retardation film or the like having an in-plane retardation of λ / 4 is used for reflection part display, but this often causes a problem that display quality of the transmission part is impaired. Arise. In the first place, such an in-plane phase difference of λ / 4 is not required in the transmission part. Nevertheless, a λ / 4 retardation film is disposed over the entire surface of the transmission part and the reflection part between the viewing-side substrate and the polarizing plate in order to correspond to the reflection part display. Further, a λ / 4 retardation film is also disposed between the substrate on the backlight side and the polarizing plate in order to compensate the transmissive portion display. This is the reason why the display quality of the transmission part is impaired. That is, in the transmission part, if the retardation of the above-mentioned λ / 4 retardation films is strictly the same, there is no influence on display quality in principle. Actually, the phase difference between the two is shifted from the manufacturing limit, which causes a decrease in contrast.

  In order to solve such a problem, a method is known in which a phase difference layer is provided inside the liquid crystal cell to give a predetermined phase difference only to the reflection portion to solve the problem.

  For example, Patent Document 1 proposes a transflective liquid crystal display device having a transmissive display region and a reflective display region in one dot region, and a retardation plate provided only in the reflective display region. . In the reflective display region, a phase difference of approximately a quarter wavelength is given.

  Further, for example, Patent Document 2 proposes a transflective liquid crystal display device having a transmissive display region and a reflective display region in one dot region and provided with a retardation plate made of a specific polymer liquid crystal. Has been. The retardation plate is made of, for example, a polymer liquid crystal aligned in different directions in the reflection region and the transmission region. Alternatively, only the reflective region is oriented in a predetermined direction, and the transmissive region is made of a polymer liquid crystal that is oriented almost randomly.

  Furthermore, Patent Document 3 proposes a retardation plate that is used by being incorporated in a liquid crystal display element having pixels composed of display areas of three colors of red, green, and blue. Such a retardation plate is formed of a polymerization type liquid crystal material with a different thickness for each fine region corresponding to the display region of each color of the pixel. Thereby, the retardation amount according to the wavelength of the light passing through the fine region is given.

  However, these conventional methods must be said to be inappropriate as a method for easily and sufficiently solving the problem of the phase difference.

  In the method described in Patent Document 1, a phase difference layer is provided only in the reflective display region to give a phase difference of approximately ¼ wavelength, and a configuration in which no phase difference layer is provided in the transmissive display region, that is, a phase difference. The layer has a predetermined film thickness in the reflective display area and is zero in the transmissive display area. A boundary portion where the retardation layer is thinner than the predetermined film thickness but not zero is inevitably generated at a position where the reflective display region and the transmissive display region are in contact with each other. Of course, this boundary part does not satisfy the optical characteristics required for the reflective display area and the optical characteristics required for the transmissive display area, so that the display characteristics of the liquid crystal display device are deteriorated.

  In the method described in Patent Document 2, the polymer liquid crystal is set in a predetermined alignment state in the reflective display region, and is formed in a different alignment state or a random alignment state in the transmissive display region. At the place where the reflective display area and the transmissive display area are in contact with each other, it is difficult to avoid a boundary portion where the alignment state of the polymer liquid crystal does not correspond to either the reflective display area or the transmissive display area. Accordingly, of course, this boundary portion naturally does not satisfy the optical characteristics required for the reflective display area and the transmissive display area, and deteriorates the display characteristics of the liquid crystal display device.

  The problem of the configuration in which a polymerization type liquid crystal material in Patent Document 3 is formed with a different film thickness for each fine region is the same as that in Patent Document 1. In the area where each micro area with different film thickness comes into contact, the boundary of the film thickness between the two micro areas is unavoidably generated, and the amount of retardation in the boundary does not match either of the colors corresponding to each micro area It becomes.

Japanese Patent No. 3788421 JP 2004-226829 A JP 2004-191832 A

  An object of the present invention is to realize a transflective liquid crystal display device that can be efficiently manufactured by a simplified method and has excellent display performance.

According to a first aspect of the present invention , comprising: a light-transmitting planar body; and a solidified liquid crystal layer supported by the planar body and formed as a continuous film made of the same material, the solidified liquid crystal layer includes: A phase difference including an anisotropic phase portion having refractive index anisotropy and an isotropic phase portion having no refractive index anisotropy, and a width of a boundary between the anisotropic phase portion and the isotropic phase portion is less than 8 μm A method for manufacturing a substrate , comprising: forming a solidified liquid crystal layer on a light-transmitting planar body directly or via another layer, wherein the solidified liquid crystal layer is formed on the planar body A film forming step of forming a liquid crystal material layer including a photopolymerizable or photocrosslinkable thermotropic liquid crystal compound, and a mesogen of the thermotropic liquid crystal compound forming an alignment structure; and a part of the liquid crystal material layer In the region, Es / Em (Es emits light with a wavelength of 200 nm to 319 nm. Illuminance, and Em is the irradiance of light having a wavelength of 320 nm to 370 nm) (5) or more, and the thermotropic liquid crystal compound is polymerized or crosslinked in the liquid crystal material layer. An exposure step of forming a first region containing a product and a second region containing the unreacted thermotropic liquid crystal compound without the reaction product, and then the thermotropic liquid crystal compound isotropic from the liquid crystal phase A development step in which the liquid crystal material layer is heated to a temperature equal to or higher than a phase transition temperature changing to a phase to substantially lose the orientation of the mesogen in the second region; and the orientation of the mesogen in the second region is approximately And a fixing step of polymerizing and / or cross-linking the unreacted thermotropic liquid crystal compound while being lost. Law is provided.

According to a second aspect of the present invention , comprising: a light-transmitting planar body; and a solidified liquid crystal layer that is supported by the planar body and formed as a continuous film made of the same material, the solidified liquid crystal layer includes: A phase difference including an anisotropic phase portion having refractive index anisotropy and an isotropic phase portion having no refractive index anisotropy, and a width of a boundary between the anisotropic phase portion and the isotropic phase portion is less than 8 μm A method for manufacturing a substrate , comprising: forming a solidified liquid crystal layer on a light-transmitting planar body directly or via another layer, wherein the solidified liquid crystal layer is formed on the planar body A film forming step of forming a liquid crystal material layer containing a photopolymerizable or photocrosslinkable thermotropic liquid crystal compound, wherein the mesogen of the thermotropic liquid crystal compound forms an alignment structure, and the liquid crystal while leaving an unexposed portion In at least two regions of the material layer, Es / Em (Es has a wavelength of 200 n Irradiance of light of 319 nm or less, Em is irradiance of light of wavelength 320 nm or more and 370 nm or less) is irradiated with light of 5 or more under different conditions, and the thermotropic liquid crystal compound is incorporated in the liquid crystal material layer A first region containing a reaction product polymerized or cross-linked, a second region containing the unreacted thermotropic liquid crystal compound without the reaction product, the reaction product and the unreacted thermotropic liquid crystal compound An exposure step of forming a third region having a content of the reaction product lower than that of the first region, and then a phase transition temperature at which the thermotropic liquid crystal compound changes from a liquid crystal phase to an isotropic phase; The liquid crystal material layer is heated to an equal temperature or higher to reduce the degree of orientation of the mesogen in at least the three regions, and in the second region, A developing step for substantially losing the orientation of the sogen, and the unreacted thermotropic liquid crystal compound while reducing the degree of orientation of the mesogen in the third region and losing the orientation of the mesogen in the second region. And a fixing step of polymerizing and / or cross-linking the phase difference substrate.

  According to the present invention, a transflective liquid crystal display device that can be manufactured by a simplified method and has excellent display performance is realized.

1 is a plan view schematically showing a liquid crystal display device according to one embodiment of the present invention. Sectional drawing along the II-II line of the liquid crystal display device shown in FIG. Sectional drawing along the III-III line of the liquid crystal display device shown in FIG. Sectional drawing along the IV-IV line of the liquid crystal display device shown in FIG. FIG. 5 is a plan view schematically showing a color filter layer included in the liquid crystal display device shown in FIGS. 1 to 4. FIG. 5 is a plan view schematically showing a solidified liquid crystal layer included in the liquid crystal display device shown in FIGS. 1 to 4. Sectional drawing which shows schematically the liquid crystal display device which concerns on one modification. Bright lines of light irradiated in the examples. Bright lines of light irradiated in the examples. Bright lines of light irradiated in the examples. Bright line of light irradiated in the comparative example. Bright line of light irradiated in the comparative example. Bright line of light irradiated in the comparative example.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, the same referential mark is attached | subjected to the component which exhibits the same or similar function through all the drawings, and the overlapping description is abbreviate | omitted.

  FIG. 1 is a plan view schematically showing a liquid crystal display device according to one embodiment of the present invention. FIG. 2 is a cross-sectional view taken along the line II-II of the liquid crystal display device shown in FIG. 3 is a cross-sectional view taken along line III-III of the liquid crystal display device shown in FIG. FIG. 4 is a cross-sectional view taken along line IV-IV of the liquid crystal display device shown in FIG. FIG. 5 is a plan view schematically showing a color filter layer included in the liquid crystal display device shown in FIGS. FIG. 6 is a plan view schematically showing a solidified liquid crystal layer included in the liquid crystal display device shown in FIGS.

  The liquid crystal display device shown in FIGS. 1 to 4 is a transflective liquid crystal display device employing an active matrix driving method. The liquid crystal display device includes an array substrate 10, a counter substrate 20, a liquid crystal layer 30, a pair of polarizing plates (not shown), and a backlight (not shown).

  The array substrate 10 includes a plane body 110. The planar body 110 is a light transmissive planar body such as a glass plate or a resin plate.

  On one main surface of the planar body 110, a pixel circuit (not shown), a scanning line (not shown), a signal line (not shown), and a pixel electrode are formed.

  Each pixel circuit includes a switching element such as a thin film transistor. The pixel circuits are arranged in a matrix on the plane body 110.

  The scanning lines are arranged corresponding to the rows of the pixel circuits. The operation of each pixel circuit is controlled by a scanning signal supplied from the scanning line.

  The signal lines are arranged corresponding to the columns of the pixel circuits. Each pixel electrode is connected to a signal line through a pixel circuit.

  Each pixel electrode includes a transparent electrode 150T and a reflective electrode 150R that are electrically connected to each other. The transparent electrode 150T includes a non-overlapping portion that does not face the reflective electrode 150R. Of each pixel, a portion corresponding to the non-overlapping portion is a transmissive display portion, and a portion corresponding to the reflective electrode 150R is a reflective display portion.

  The transparent electrode 150T is made of a transparent conductor. As the transparent conductor, for example, transparent conductive oxides such as indium tin oxide and tin oxide can be used.

  The reflective electrode 150R is made of a metal or an alloy. As the metal or alloy, for example, aluminum, silver, or an alloy thereof can be used.

  Typically, the reflective electrode 150R is formed on the transparent electrode 150T. Thereby, the reflective electrode 150R and the transparent electrode 150T are electrically connected. Instead, the transparent electrode 150T may be formed on the reflective electrode 150R. Alternatively, the reflective electrode 150R and the transparent electrode 150T may be electrically connected via another conductor.

  The pixel electrode is covered with an alignment film 160. The alignment film 160 is, for example, a vertical alignment film. As a material of the alignment film 160, for example, a transparent resin layer such as polyimide can be used.

  The counter substrate 20 includes a planar body 210. The planar body 210 faces the alignment film 160. The planar body 210 is a light transmissive planar body such as a glass plate or a resin plate.

  A color filter layer 220, a solidified liquid crystal layer 230, a counter electrode 250, and an alignment film 260 are formed in this order on the surface of the planar body 210 facing the alignment film 160.

  The color filter layer 220 includes a plurality of unit regions arranged on one main surface of the plane body 210. Each unit region includes, for example, first to third colored pixels arranged on the previous main surface, and further has a reflective display region and a transmissive display region, respectively.

  The first to third colored pixels may be separated from each other by a black separation wall 270. The reflective display region and the transmissive display region in each colored pixel may also be separated from each other by the black separation wall 270.

  The first colored pixels 220a face part of the transparent electrodes 150T. The first colored pixels 220a each extend in the Y direction, or are adjacent to each other via the black separation wall 270 in the Y direction, and form a plurality of strip-like patterns arranged in the X direction. The X direction and the Y direction are directions parallel to the main surface of the planar body 210 and intersecting each other. The Z direction is a direction orthogonal to the X direction and the Y direction.

The first colored pixel 220a includes a first reflective display region 220a _R and a first transmissive display region 220a _T. The first reflective display region 220a _R has a higher light transmittance than the first transmissive display region 220a _T.

The first reflective display region 220a _R is provided at a position corresponding to a portion where the reflective electrode 150R is formed in the transparent electrode 150T facing the first colored pixel 220a. The first transmissive display region 220a _T is provided at a position corresponding to a portion exposed from the reflective electrode 150R in the transparent electrode 150T facing the first colored pixel 220a.

  The second colored pixel 220b faces another part of the transparent electrode 150T. The second colored pixels 220b each extend in the Y direction, or are adjacent to each other via the black separation wall 270 in the Y direction, and form a plurality of strip-like patterns arranged in the X direction.

Second colored pixel 220b includes a second reflective display region 220b _R and a second transmissive display region 220b _T. The second reflective display region 220b _R has a higher light transmittance than the second transmissive display region 220b _T.

The second reflective display region 220b _R is provided at a position corresponding to a portion where the reflective electrode 150R is formed in the transparent electrode 150T facing the second colored pixel 220b. The second transmissive display region 220b _T, of the transparent electrode 150T of the second colored pixel 220b are opposed, are provided at positions corresponding to the portion exposed from the reflective electrodes 150R.

  The third colored pixel 220c faces another part of the transparent electrode 150T. The third colored pixels 220c each extend in the Y direction, or are adjacent to each other via the black separation wall 270 in the Y direction, and form a plurality of strip-like patterns arranged in the X direction.

Third colored pixel 220c includes a third reflective display region 220c _R and a third transmissive display region 220c _T. The third reflective display region 220c _R is greater than the transmittance of light as compared to the third transmissive display region 220c _T.

The third reflective display region 220c _R, of the transparent electrode 150T to third colored pixel 220c is facing, is provided at a position corresponding to the portion where the reflective electrode 150R is formed. Third transmissive display region 220c _T, of the transparent electrode 150T to third colored pixel 220c is facing, is provided at a position corresponding to the portion exposed from the reflective electrodes 150R.

The wavelength of light mainly transmitted through the second reflective display region 220b _R is shorter than that of the first reflective display region 220a _R when irradiated with white light, and the third reflective display region portion 220c _R Longer compared. Further, the wavelength of light mainly transmitted by the second transmissive display region 220b _T is similarly shorter than that of the first transmissive display region 220a _T and more than that of the third transmissive display region 220c _T. long.

Here, as an example, each of the first reflective display region 220a _R and the first transmissive display region 220a _T is a red colored layer, and the second reflective display region 220b _R and the second transmissive display region 220b _T each is green colored layer, each of the third reflective display region 220c _R and the third transmissive display region 220c _T is assumed to be a blue color layer.

  The solidified liquid crystal layer 230 is a retardation layer. The solidified liquid crystal layer 230 is stacked on the color filter layer 220 provided on the planar body 210. The solidified liquid crystal layer 230 is typically a continuous film. The solidified liquid crystal layer 230 is formed, for example, by polymerizing and / or crosslinking a thermotropic liquid crystal compound. The thermotropic liquid crystal compound can be made into a composition by adding predetermined components. The solidified liquid crystal layer 230 is typically a continuous film having substantially the same thickness over the entire surface of the substrate.

  An alignment film may be interposed between the solidified liquid crystal layer 230 and the color filter layer 220. As this alignment film, for example, a resin layer in which an alignment process such as a rubbing process or an optical alignment process is uniformly performed on the entire surface can be used. As this resin layer, for example, a polyimide layer can be used.

  A layer other than the alignment film may be interposed between the solidified liquid crystal layer 230 and the color filter layer 220. For example, a structure in which a flattening layer that reduces unevenness of this layer is formed on the color filter layer 220, and the solidified liquid crystal layer 230 is stacked directly on the flattening layer or via an alignment film may be used. .

  The solidified liquid crystal layer 230 has 230R and 230T including regions 230Ra, 230Rb, and 230Rc. Each of the regions 230Ra, 230Rb, 230Rc and 230T is a region extending from one main surface of the solidified liquid crystal layer 230 to the other main surface. The regions 230R and 230T are adjacent to each other in the direction perpendicular to the Z direction via the boundary 230H. In the region 230R, the regions 230Ra, 230Rb, and 230Rc are adjacent to each other in the direction perpendicular to the Z direction via the boundary 230H.

Region 230Ra, among the solidified liquid crystal layer 230, a region corresponding to the first reflective display region 220a _R. Similarly, the region 230Rb is a region corresponding to the second reflective display region 220b _R, region 230Rc is a region corresponding to the third reflective display region 220c _R. That is, 230R including the regions 230Ra, 230Rb, and 230Rc is a reflective display region corresponding to each reflective display region of the first to third colored pixels in the color filter layer 220. In each of the regions 230Ra, 230Rb, and 230Rc, the degree of mesogen orientation is substantially uniform.

  Here, “degree of orientation of mesogen” in a certain region means the degree of orientation of mesogen in that region. The degree of orientation of the mesogen may be constant throughout the region, or may vary along the Z direction. For example, in a certain region, the degree of orientation may be higher near the lower surface, and the degree of orientation may be lower near the upper surface. In this case, “degree of orientation of mesogen” indicates an average of the degree of orientation of mesogen in the thickness direction. It can be confirmed by comparing the refractive index anisotropy of a certain region that the degree of orientation is larger than that of another region.

  The degree of mesogen orientation can be the same over all regions 230Ra, 230Rb, and 230Rc. Alternatively, the degree of orientation of one of the regions 230Ra, 230Rb, and 230Rc may be different from that of the remaining two regions. Alternatively, these three regions can all have different degrees of orientation from other regions. For example, the region 230Ra has a higher degree of mesogen orientation than the region 230Rb, and the region 230Rb can have a higher degree of mesogen orientation than the region 230Rc. In this case, the region 230Ra has a larger refractive index anisotropy than the region 230Rb, and the region 230Rb has a larger refractive index anisotropy than the region 230Rc.

  As described above, the solidified liquid crystal layer 230 of the present invention has different refractive index anisotropy, i.e., birefringence, by varying the degree of orientation depending on the region, and thus has a different phase difference depending on each region. Can be granted. When the thickness of the solidified liquid crystal layer 230 is almost equal over the entire surface of the substrate, the phase difference in each region is proportional to the birefringence of each region.

The region 230T is a region of the solidified liquid crystal layer 230 corresponding to the first transmissive display region 220a _T , the second transmissive display region 220b _T, and the third transmissive display region 220c _T. That is, the region 230T is a transmissive display region corresponding to the transmissive display region of each of the first to third colored pixels of the color filter layer 220.

  In the region 230T, typically, the mesogen does not form a specific alignment structure, that is, is fixed in a random alignment state. That is, the region 230T is typically optically isotropic.

  The boundary 230 </ b> H is a band-shaped region that exists between the reflective display region 230 </ b> R and the transmissive display region 230 </ b> T in the solidified liquid crystal layer 230 and exhibits intermediate refractive index anisotropy between the two regions. More specifically, when the region 230T is isotropic and the birefringence is 0 and the birefringence of the region 230R is X, the region has a birefringence of 0.1X to 0.9X. . In the solidified liquid crystal layer 230 in the embodiment of the present invention, the width of the boundary 230H is less than 8 μm.

  In the case where the degrees of orientation of the regions 230Ra, 230Rb, and 230Rc are made different from each other, the boundary 230H similarly exists between the regions. For example, if the region 230Ra has a higher degree of mesogen orientation than the region 230Rb, that is, the birefringence is larger, the birefringence of the region 230Ra is Xa, and the birefringence of the region 230Rb is Xb. The boundary 230H is a region having a birefringence of (0.1Xa + 0.9Xb) or more and (0.9Xa + 0.1Xb) or less. In this case as well, in the embodiment of the present invention, in the solidified liquid crystal layer 230, the width of the boundary 230H is less than 8 μm.

When the reflective display regions 220a _R , 220b _R , and 220c _{R of the} color filter layer 220 are separated from the transmissive display regions 220a _T , 220b _T , and 220c _T by the black separation wall 270, the boundary 230H Corresponds to all or part of the black separation wall 270. That is, the width of the boundary 230H is the same as or narrower than the width of the black separation wall 270.

  Here, as an example, it is assumed that the regions 230Ra to 230Rc are uniaxial, and their slow axes form an angle of 45 ° in the X direction and the Y direction. In addition, here, the phase difference of the region 230Ra is ¼ of the wavelength of the red light transmitted through the first colored pixel 220a, and the phase difference of the region 230Rb is the wavelength of the green light transmitted through the second colored pixel 220b. The phase difference of the region 230Rc is ¼ of the center wavelength of the blue light transmitted by the third colored pixel 220c.

  The counter electrode 250 is formed on the solidified liquid crystal layer 230. The counter electrode 250 is a continuous film extending over the entire display area. The counter electrode 250 is made of the transparent conductor described above, for example.

  The alignment film 260 covers the counter electrode 250. The alignment film 260 is a vertical alignment film, for example. As a material of the alignment film 260, for example, a transparent resin layer such as polyimide can be used.

  In addition to the color filter layer 220, the black separation wall 270, and the solidified liquid crystal layer 230, other components may be formed on the plane body 210. For example, the planar body 210 may further include columnar spacers that keep the layer thickness of the liquid crystal layer 30 constant. Furthermore, the planar body 210 may be formed with protrusions for controlling the alignment of mesogens of liquid crystal molecules contained in the liquid crystal layer 30.

  The array substrate 10 and the counter substrate 20 are bonded together via a frame-shaped adhesive layer (not shown). The array substrate 10, the counter substrate 20, and the adhesive layer form a hollow structure.

  The liquid crystal layer 30 is made of a liquid crystal compound or a liquid crystal composition. This liquid crystal compound or liquid crystal composition has fluidity and fills a space surrounded by the array substrate 10, the counter substrate 20, and the adhesive layer. The array substrate 10, the counter substrate 20, the adhesive layer, and the liquid crystal layer 30 form a liquid crystal cell.

  Here, as an example, the liquid crystal compound included in the liquid crystal layer 30 is a liquid crystal molecule having a negative dielectric anisotropy including a rod-shaped mesogen, and the mesogen of the liquid crystal molecule is substantially parallel to the Z direction when no voltage is applied. Is oriented. In addition, when a voltage is applied, the mesogens of the liquid crystal molecules tilt from the Z direction in a direction that forms an angle of 45 ° in the X direction and the Y direction, or substantially parallel to a direction that forms an angle of 45 ° in the X direction or the Y direction. Let it be oriented.

  The polarizing plates are attached to both main surfaces of the liquid crystal cell. Here, as an example, these polarizing plates are linear polarizing plates, and their transmission axes are orthogonal, one of which is parallel to the X direction and the other is parallel to the Y direction. Suppose it is placed.

  The backlight faces the array substrate 10 with a polarizing plate in between. For example, the backlight irradiates white light toward the liquid crystal cell.

  In this liquid crystal display device, the phase difference of each of the regions 230Ra, 230Rb, and 230Rc can be arbitrarily set. Therefore, a pixel having a color that mainly transmits light having a shorter wavelength has a lower phase difference corresponding thereto, and a pixel having a color that transmits light having a longer wavelength mainly has a higher phase difference corresponding thereto. . For example, the region 230Ra can serve as a quarter-wave plate for light that has substantially the same wavelength as the light that the first colored pixel 220a mainly transmits when irradiated with white light. In addition, the region 230Rb can serve as a quarter-wave plate for light that is substantially the same in wavelength as the light that the second colored pixel 220b mainly transmits when irradiated with white light. In addition, the region 230Rc can serve as a quarter-wave plate for light that has substantially the same wavelength as the light that the third colored pixel 220c mainly transmits when irradiated with white light. Therefore, for example, optimal optical compensation can be achieved in all the reflective display regions.

  Further, in this liquid crystal display device, the region 230T can be made optically isotropic, for example. Therefore, the contrast ratio achieved by the transmissive display is not lowered due to the provision of the solidified liquid crystal layer 230.

  Further, in this liquid crystal display device, the boundary 230H inevitably generated in the solidified liquid crystal layer 230 in which the phase difference pattern is formed depending on the presence or absence of the alignment structure is suppressed to be very small. Specifically, the width of the boundary 230H is less than 8 μm. Further, when the region of the color filter layer 220 is separated by the black separation wall 270, the boundary 230 </ b> H corresponds to all or a part of the black separation wall 270. That is, the width of the boundary 230H is the same as or narrower than the width of the black separation wall 270, and the boundary 230H is hidden by the black separation wall 270 when the liquid crystal display device is viewed from the front. Therefore, in this liquid crystal display device, it is possible to minimize a decrease in display performance due to the boundary 230H.

  Thus, the above-described transflective liquid crystal display device can be manufactured by a simplified method and achieves excellent display performance.

  Various modifications can be made to this liquid crystal display device.

  FIG. 7 is a cross-sectional view schematically showing a liquid crystal display device according to a modification.

  This liquid crystal display device is the same as the liquid crystal display device described with reference to FIGS. 1 to 6 except that the solidified liquid crystal layer 230 is interposed between the planar body 210 and the color filter layer 220. .

  For example, the color filter layer 220 may be provided on the plane body 110 side. That is, the array substrate 10 may be provided with a color filter function.

  Furthermore, the solidified liquid crystal layer 230 may be provided on the planar body 110 side. In other words, the array substrate 10 may be provided with an optical compensation function.

  Next, a method for manufacturing the counter substrate 20 included in the liquid crystal display device described with reference to FIGS. 1 to 6 will be described. The counter substrate 20 included in the liquid crystal display device of FIG. 7 is manufactured by a method substantially similar to the following method, except that the stacking order of the color filter layer 220 and the solidified liquid crystal layer 230 is reversed. Can do.

  First, a light transmissive planar body 210 is prepared. The light transmissive planar body 210 is typically a light transmissive substrate such as a glass plate or a resin plate. As a material of the glass plate, for example, soda lime glass, low alkali borosilicate glass or non-alkali aluminoborosilicate glass can be used. As a material for the resin plate, for example, polycarbonate, polyacrylate, polymethacrylate, cyclic polyolefin, cellulose ester, polyethylene terephthalate, or the like can be used. Further, the planar body 210 is not necessarily rigid, and may be a light transmissive film or sheet, for example.

  Next, a black separation wall 270 is formed on the light-transmitting planar body 210 by the following method or the like.

  The black separation wall 270 is obtained, for example, by applying a black coloring composition to form a predetermined pattern and curing it. The black coloring composition includes a black pigment and a pigment carrier, and examples of the black pigment include carbon black.

  Specifically, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, #, manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black 339, Diamond Black S Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR; Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908, carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66 manufactured by Asahi Carbon Co., Ltd. 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa carbon Black ColorBlackFw200, ColorBlackFw2, C lorBlackFw2V, ColorBlackFw1, ColorBlackFw18, ColorBlackS170, ColorBlackS160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140V (both trade names), and the like.

  It is also possible to use inorganic pigments as pigments, specifically, metal oxides such as yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, etc. Examples thereof include powders, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with carbon black in order to ensure good coatability, sensitivity, developability and the like while maintaining light shielding properties.

  The pigment carrier contained in the black coloring composition is for dispersing the pigment, and is composed of a resin, a precursor thereof, or a mixture thereof. Examples of the resin include a thermoplastic resin, a thermosetting resin, and a photosensitive resin. The precursor includes a polyfunctional monomer or oligomer that is cured by irradiation with radiation to form a resin. These can be used alone or in admixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Photosensitive resins include linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups, acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups, epoxy groups, and the like. A methacrylic compound having a reactive substituent or a cinnamic acid can be reacted to introduce a resin in which a photocrosslinkable group such as an acryloyl group, a methacryloyl group, and a styryl group is introduced into the linear polymer. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer and an α-olefin-maleic anhydride copolymer is used as an acrylic compound or methacrylic compound having a hydroxyl group such as hydroxyalkyl acrylate and hydroxyalkyl methacrylate. Resins half-esterified with a compound can also be used.

  Examples of the monomer and / or oligomer that is a precursor of the resin include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, and polyethylene glycol diacrylate. , Polyethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tricyclodecanyl acrylate, tricyclodecanyl Methacrylate, melami Various acrylic esters and methacrylic esters such as acrylate, melamine methacrylate, epoxy acrylate, and epoxy methacrylate, acrylic acid, methacrylic acid, styrene, vinyl acetate, acrylamide, methacrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide , And acrylonitrile. These resins can be used alone or in admixture of two or more.

  The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the pigment in the black coloring composition. Moreover, when using the mixture of resin and its precursor as a pigment carrier, resin is 20-400 weight part with respect to 100 weight part of pigments in a black coloring composition, Preferably it is 50-250 weight part. Can be used in quantities. Moreover, the precursor of transparent resin can be used in the quantity of 10-300 weight part with respect to 100 weight part of pigments in a black coloring composition, Preferably it is 10-200 weight part.

  When the black composition is cured by irradiation with ultraviolet rays or the like, a photopolymerization initiator and, in some cases, a sensitizer are added to the composition.

  As the photopolymerization initiator, for example, the following compounds can be used. 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Acetophenones such as methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin photopolymerization initiators such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, Benzophenone-based photopolymerization initiators such as hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Photopolymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl -S-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloro) Triazine-based photopolymerization initiators such as methyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate type A photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, and the like.

  A photoinitiator can be used individually or in mixture of 2 or more types. The content is preferably 5 to 200 parts by weight and more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the pigment in the black coloring composition.

  A sensitizer may be used together with the photopolymerization initiator. Examples of the sensitizer include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethyliso Examples include phthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4′-diethylaminobenzophenone.

  The sensitizer can be contained in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  The black coloring composition may further contain a chain transfer agent such as a functional thiol.

  A polyfunctional thiol is a compound having two or more thiol groups. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2- (N, N Dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in admixture of two or more.

  The polyfunctional thiol can be used in an amount of 0.2 to 150 parts by weight, preferably 0.2 to 100 parts by weight, with respect to 100 parts by weight of the pigment in the black coloring composition.

  The black coloring composition may further contain a solvent. When a solvent is used, the dispersibility of the pigment can be improved. Therefore, it becomes easy to apply the black coloring composition on the planar body 210 so that the dry film thickness is, for example, 0.2 to 5 μm. .

  Examples of the solvent include the following compounds. Ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and di- Ether solvents such as propylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, and n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monomethyl Cellsolve solvents such as ether acetate; methanol, ethanol, iso-propanol, n-propanol, iso-butanol, n-butanol, And alcohol solvents such as amyl alcohol; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpenes such as terpine oil, D-limonene, and pinene Hydrocarbon oils; paraffinic solvents such as mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso # 100 (Exxon Chemical Co., Ltd.); halogens such as carbon tetrachloride, chloroform, trichlorethylene, and dichloromethane Halogenated aromatic hydrocarbon solvent such as chlorobenzene, carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, tetrahydrofuran, N, N-dimethylformamide, and Is N- methylpyrrolidone. Among these, ketones or cellosolve solvents are preferable. These solvents can be used alone or as a mixed solvent of two or more.

  The amount of the solvent used is preferably 800 to 4000 parts by weight and more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the black coloring composition.

  An appropriate amount of a plasticizer, a thermal polymerization initiator, a surfactant, a storage stabilizer, a polymerization inhibitor, an adhesion improver, and the like can be further added to the black coloring composition as necessary.

  Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didecyl phthalate, trioctyl trimellitate, tetraoctyl pyromellitate, tetraoctyl biphenyl tetracarboxylate, dioctyl adipate, diisononyl adipate, dioctyl sebacate, dioctyl azelate, And alkyl esters of aliphatic or aromatic polycarboxylic acids such as trioctyl citrate, phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, aliphatic or aromatic polycarboxylic acids and glycols Polyester obtained by condensing epoxide, epoxidized soybean oil, epoxidized fatty acid octyl ester, epoxy compound such as epoxy resin, polyether polyol, polyether Min, and polyether compounds such as polyether esters. If necessary, the end of such a compound may be blocked with a monohydric alcohol and / or a monovalent carboxylic acid.

  Moreover, the following compounds can also be used as a plasticizer. Chlorinated paraffin, polyethylene, ethylene-vinyl acetate copolymer, polyether ester, ethylene-acrylic acid copolymer, ionomer, ethylene-acrylic ester copolymer, ethylene-methacrylic ester copolymer, polypropylene, polystyrene, poly α -Methylstyrene, α-methylstyrene-vinyltoluene copolymer, styrene-butadiene copolymer, styrene-methylmethacrylate copolymer, styrene-methacrylic acid copolymer, styrene-acrylonitrile copolymer, styrene-acrylate copolymer Blend, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, methyl methacrylate-methacrylate copolymer, 2 -Ethylhexyl acrylate-methacrylate copolymer, ethyl acrylate-acrylic acid copolymer, methyl methacrylate-methacrylic acid polymer, polyvinyl acetate, vinyl acetate-vinyl chloride copolymer, polyvinyl chloride, polyvinylidene chloride, vinylidene chloride- Thermoplastic resins such as vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, polyacrylonitrile, ABS resin, polycarbonate, polyamide, polyphenylene sulfide, polyphenylene oxide, polyvinyl butyral, polyvinyl formal, polyacetal, polyurethane, ethyl cellulose, cellulose acetate, Metal soap such as zinc stearate and calcium stearate.

  Examples of the thermal polymerization initiator include benzoyl peroxide (BPO), t-butylperoxy-2-ethylhexanate (PBO), di-t-butyl peroxide (PBD), t-butylperoxyisopropyl carbonate ( PBI), and peroxide initiators such as n-butyl 4,4, bis (t-butylperoxy) valerate (PHV); 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylpropane), 2,2′-azobis (2-methylbutane), 2, 2'-azobis (2-methylpentane), 2,2'-azobis (2,3-dimethylbutane), 2,2'-azobis (2-methylhexane), 2,2 ' Azobis (2,4-dimethylpentane), 2,2′-azobis (2,3,3-trimethylbutane), 2,2′-azobis (2,4,4-trimethylpentane), 3,3′-azobis (3-methylpentane), 3,3′-azobis (3-methylhexane), 3,3′-azobis (3,4-dimethylpentane), 3,3′-azobis (3-ethylpentane), dimethyl- 2,2′-azobis (2-methylpropionate), diethyl-2,2′-azobis (2-methylpropionate), and di-tert-butyl-2,2′-azobis (2-methylpropionate) An azo-based initiator such as Pionate) can be used.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate. , Anionic surface activity such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Nonionic surfactants such as ethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts, alkyl Examples include amphoteric surfactants such as alkylbetaines such as dimethylaminoacetic acid betaine and alkylimidazolines. The surfactants as described above may be used alone or in combination of two or more.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include phosphine and phosphite.

  Examples of the polymerization inhibitor include 2,6-di-t-butyl-p-cresol, 3-t-butyl-4-hydroxyanisole, 2-t-butyl-4-hydroxyanisole, and 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4, 4′-thiobis (3-methyl-6-tert-butylphenol), styrenated phenol, styrenated p-cresol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Tetrakis [methylene-3- (3 ′, 5′-di-1-butyl-4′-hydroxyphenyl) propionate] methane, octadecyl 3- (3,5- -T-butyl-4-hydroxyphenylpropionate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,2 ' -Dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethyldiphenylmethane, 4,4'-methylenebis (2,6-di-t-butylphenol), tris (3,5-di- t-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzoyl) isocyanurate, bis [2-methyl-4- (3 -N-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, 1-oxy-3-methyl-isopropylbenzene, 2,5-di-t-butylhydroquino 2,2'-methylenebis (4-methyl-6-nonylphenol), alkylated bisphenol, 2,5-di-t-amylhydroquinone, polybutylated bisphenol A, bisphenol A, 2,6-di-t-butyl -P-ethylphenol, 2,6-bis (2'-hydroxy-3-t-butyl-5'-methyl-benzyl) -4-methylphenol, 1,3,5-tris (4-t-butyl- 3-hydroxy-2,6-dimethylbenzyl) isocyanurate, terephthaloyl broth (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl sulfide), 2,6-di-tert-butylphenol, 2, 6-di-t-butyl-α-dimethylamino-p-cresol, 2,2′-methylene-bis (4-methyl-6-cyclohexylphenol) Toluethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], hexamethylene glycol-bis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxytoluene, 6- (4-hydroxy-3,5-di-t-butylaniline) -2,4-bis (octylthio) -1,3,5-triazine N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyl-phosphoric acid diethyl ester, 2,4 -Dimethyl-6-t-butylphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butyl) Tilphenol), tris [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanurate, 2,4,6-tributylphenol, bis [3,3-bis (4 ′ -Hydroxy-3'-tert-butylphenyl) -butyric acid] glycol ester, 4-hydroxymethyl-2,6-di-tert-butylphenol, and bis (3-methyl-4-hydroxy-5-tert-butyl) Examples thereof include phenolic inhibitors such as benzyl) sulfide.

  N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, 2 , 2,4-trimethyl-1,2-dihydroquinoline polymer, amine-based inhibitors such as diaryl-p-phenylenediamine, dilauryl thiodipropionate, distearyl thiodipropionate, 2-mercaptobenzimidazole Sulfur-based inhibitors such as diol, phosphorus-based inhibitors such as distearyl pentaerythritol diphosphite can also be used.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane; (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxysilanes such as epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N -Β (aminoethyl) γ- Minopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane And aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane; and silane coupling agents such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The black coloring composition can be prepared, for example, in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, ink jet printing ink, solvent developing type or alkali developing type coloring resist. The colored resist can be prepared by dispersing a dye in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and an organic solvent. The pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the black coloring composition (100% by weight). More preferably, it is contained in a proportion of 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by a pigment carrier.

  The black colored composition is produced by means of, for example, centrifugation, sintering filter, membrane filter, etc., coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust Is preferably removed.

  When the printing method is employed, the black separation wall 270 can be patterned simply by printing the black coloring composition prepared as the above-described various printing inks and drying it. Therefore, the printing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the composition does not dry or solidify the ink on the printing plate or on the blanket. Control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted with a dispersant or extender pigment.

  When the black separation wall 270 is formed by photolithography, a black colored composition prepared as a solvent development type or alkali development type colored resist is used. Such a black colored composition is applied onto the planar body 210 by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 10 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  If necessary, the dried coating film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the coating film. Thereafter, the film is immersed in a solvent or an alkali developer and subjected to development processing. The developing process may be performed by spraying a predetermined developer by spraying or the like. The uncured portion is removed by development processing to form a desired pattern, and the black separation wall 270 can be obtained. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, the black separation wall 270 with higher accuracy than the above-described printing method can be manufactured.

  Examples of the alkaline developer include aqueous solutions such as sodium carbonate and sodium hydroxide. Alternatively, organic alkalis such as dimethylbenzylamine and triethanolamine can be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In addition, in order to improve ultraviolet exposure sensitivity, you may form the film | membrane which prevents the superposition | polymerization inhibition by oxygen after apply | coating and drying the above-mentioned black coloring composition. For example, the target film can be formed by applying and drying a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin.

  The black separation wall 270 can be formed by an electrodeposition method, a transfer method, or the like in addition to the method described above. The electrodeposition method is a method in which a separation wall is electrodeposited on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a planar body. The transfer method is a method in which a black separation wall is formed in advance on the surface of a peelable transfer base sheet, and this is transferred to a desired flat body.

  The black separation wall 270 may be formed of a metal thin film such as a chromium thin film, not a black coloring composition in which a black pigment is dispersed in a pigment carrier. As a means for forming a metal thin film on a planar body, for example, a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, a thermal spraying method, an electrodeposition method, a chemical plating method, a molten plating method, and other known methods are used. be able to.

  The obtained metal thin film is exposed after a photosensitive composition film is formed on the metal thin film, and unnecessary portions are removed by etching to obtain a desired pattern.

  The method of performing exposure after providing a film of the photosensitive composition on the upper portion and removing the unnecessary portions by etching, as a matter of course, can be used as a means for obtaining a predetermined pattern on the coating film of the black colored composition.

  The color filter layer 220 is formed on the plane body 210 on which the black separation wall 270 is formed in this manner by the method described below.

  Any method may be used to form the color filter layer 220. According to an example, a color filter layer is formed by applying a color coloring composition containing a pigment carrier and a color pigment dispersed therein to form a predetermined pattern, and curing this to obtain a colored pixel, and a color filter layer. 220 can be formed.

  As a pigment contained in the color coloring composition, an organic pigment and / or an inorganic pigment can be used. The color coloring composition may contain one kind of organic or inorganic pigment, and may contain a plurality of kinds of organic pigments and / or inorganic pigments.

  The pigment preferably has high color developability and high heat resistance, particularly high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for a color coloring composition is shown with a color index number.

  Examples of the organic pigment of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 179, 184, 185, Red pigments such as 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272 and 279 can be used. As the organic pigment of the red coloring composition, a mixture of a red pigment and a yellow pigment may be used.

  Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 It can be used 182,185,187,188,193,194,199,198,213 and 214 or the like.

  Examples of the organic pigment of the green coloring composition include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. As the organic pigment of the green coloring composition, a mixture of a green pigment and a yellow pigment may be used. As this yellow pigment, the thing similar to having illustrated about the red coloring composition can be used, for example.

  Examples of the organic pigment of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. As an organic pigment of the blue coloring composition, a mixture of a blue pigment and a purple pigment may be used. Examples of the purple pigment include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 or 50 can be used.

  Examples of inorganic pigments include, for example, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, and cobalt green metal oxide powder, metal sulfide powder, or Metal powder etc. can be used. Inorganic pigments can be used in combination with organic pigments, for example, in order to achieve good coatability, sensitivity, developability, and the like while balancing chroma and lightness.

  The color coloring composition may further contain a coloring component other than the pigment. For example, the coloring composition may contain a dye as long as sufficient heat resistance can be achieved. In this case, toning using a dye is possible.

  The pigment carrier contained in the above-described color coloring composition is composed of a resin, a precursor thereof, or a mixture thereof. Examples of the resin include thermoplastic resins, thermosetting resins, and photosensitive resins, and precursors thereof include polyfunctional monomers or oligomers that are cured by irradiation with radiation to form a resin. These can be used alone or in admixture of two or more.

  As resins such as thermoplastic resins, thermosetting resins and photosensitive resins, polyfunctional monomers and oligomers which are precursors of resins, the same compounds as those used in the black coloring composition described above can be used. The amount used is also substantially the same as that of the black coloring composition.

  When the color coloring composition is cured by irradiation with light such as ultraviolet rays, for example, a photopolymerization initiator is added to the color coloring composition, and a sensitizer is added in some cases.

  As the photopolymerization initiator and the sensitizer, the same compounds as those used for the black colored composition described above can be used. The amount used is also substantially the same as that of the black coloring composition.

  The color coloring composition may further contain a chain transfer agent such as a polyfunctional thiol.

  As a chain transfer agent, the thing similar to the compound used for the black coloring composition mentioned above can be used. The amount used is also substantially the same as that of the black coloring composition.

  The color coloring composition may further contain a solvent. When a solvent is used, the dispersibility of the pigment can be improved. Therefore, it is easy to apply the color coloring composition on the planar body 210 so that the dry film thickness is, for example, 0.2 to 5 μm. .

  As a solvent, the thing similar to the compound used for the black coloring composition mentioned above can be used. The amount used is also substantially the same as that of the black coloring composition.

  The color coloring composition is, for example, a dispersion of three or more types of pigments such as a three roll mill, a two roll mill, a sand mill, a kneader and an attritor in a pigment carrier and an organic solvent together with the photopolymerization initiator as necessary. It can be manufactured by finely dispersing using an apparatus. The coloring composition containing two or more kinds of pigments may be produced by preparing a dispersion containing different pigments and mixing the dispersions.

  When the pigment is dispersed in the pigment carrier and the organic solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant and a pigment derivative can be used. The dispersion aid improves the dispersibility of the pigment and suppresses reaggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing a pigment in a pigment carrier and an organic solvent using a dispersion aid is used, a color filter having excellent transparency can be obtained.

  The dispersion aid is used in the coloring composition in an amount of, for example, 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

  The resin-type pigment dispersant includes a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier. The resin type pigment dispersant is adsorbed on the pigment and stabilizes the dispersibility of the pigment on the pigment carrier.

  Examples of the resin-type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid partial amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid. Acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates and hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and Oil dispersants such as salts thereof; acrylic acid-styrene copolymer, methacrylic acid-styrene copolymer, acrylic acid-acrylic acid ester copolymer, acrylic acid-methacrylic acid ester copolymer, methacrylic acid-acrylic acid ester Copolymer, methacrylate Water-soluble resins or water-soluble polymer compounds such as acid-methacrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol and polyvinylpyrrolidone; polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, Phosphate esters or a mixture containing two or more of them can be used.

  As the surfactant, the same compounds as those used for the black colored composition described above can be used.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. The pigment derivative preferably has a hue close to that of the pigment to be used, but the hue may be different if the addition amount is small. The term “organic dye” includes pale yellow aromatic polycyclic compounds such as naphthalene-based and anthraquinone-based compounds that are not generally called dyes, in addition to compounds generally called dyes. Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. Can be used. In particular, a pigment derivative having a basic group has a large effect of enhancing the dispersibility of the pigment. The coloring composition may contain one kind of dye derivative or may contain a plurality of dye derivatives.

  If necessary, an appropriate amount of a plasticizer, a thermal polymerization initiator, a storage stabilizer, a polymerization inhibitor, an adhesion improver and the like can be added to the color coloring composition. These may be the same as the compounds used for the black colored composition described above.

  The color coloring composition is the same as that of the black coloring composition, such as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, ink jet printing ink, solvent developing type or alkali developing type coloring resist. The form can be prepared by applying the same treatment.

  In addition, as a method for obtaining the color filter layer 220 from the color coloring composition, the same method as in the case of the black coloring composition can be used.

  The color filter layer 220 can also be formed by an ink jet method. When the color filter layer 220 is formed by the ink jet method, for example, ink is ejected from a nozzle toward a region partitioned by the black separation wall with respect to a black separation wall previously formed on the plane body 210. Thus, each colored pixel is obtained.

  Next, a method for forming the solidified liquid crystal layer 230 will be described.

  As the solidified liquid crystal layer 230, for example, a liquid crystal material layer containing a photopolymerizable or photocrosslinkable thermotropic liquid crystal material is formed on the color filter layer 220, and this liquid crystal material layer is subjected to pattern exposure and heat treatment. Obtain by offering. For example, the liquid crystal material layer is formed so that mesogens are aligned in one direction parallel to the main surface of the planar body 210.

  The liquid crystal material layer is obtained, for example, by applying a coating liquid containing a thermotropic liquid crystal compound on the color filter layer 120 and drying the coating film as necessary.

  Examples of the thermotropic liquid crystal compounds include alkylcyanobiphenyl, alkoxybiphenyl, alkylterphenyl, phenylcyclohexane, biphenylcyclohexane, phenylbicyclohexane, pyrimidine, cyclohexanecarboxylic acid ester, halogenated cyanophenol ester, alkylbenzoic acid ester, alkylcyano. Tolane, dialkoxytolane, alkylalkoxytolane, alkylcyclohexyltolane, alkylbicyclohexane, cyclohexylphenylethylene, alkylcyclohexylcyclohexene, alkylbenzaldehyde azine, alkenylbenzaldehyde azine, phenylnaphthalene, phenyltetrahydronaphthalene, phenyldecahydronaphthalene, derivatives thereof, Or it Acrylate compounds may be used. These liquid crystal compounds may be used alone or in combination of two or more.

  In addition to the thermotropic liquid crystal compound, the coating liquid includes a liquid crystal material layer coated with a composition containing the liquid crystal compound, for example, a solvent, a photopolymerization initiator, a sensitizer, a chain transfer agent, and a chiral agent. It can be added as long as the liquid crystal properties are not lost.

  As the solvent, the same compounds as those used for the black coloring composition described above can be used, and 100 to 3000 parts by weight, preferably 200 to 1000 parts by weight, with respect to 100 parts by weight of the liquid crystal compound in the coating liquid. Can be used.

  As the photopolymerization initiator, the same compounds as those used in the above-described black coloring composition can be used, and 0.1 to 30 parts by weight, preferably 0 to 100 parts by weight of the liquid crystal compound in the coating liquid. .3-10 parts by weight can be used.

  A sensitizer may be used in combination with a photopolymerization initiator, and for this, the same compounds as those used for the black colored composition described above can be used. The sensitizer can be contained in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  As the chain transfer agent, the same compounds as those used for the black colored composition described above can be used, and 0.2 to 30 parts by weight, preferably 0, based on 100 parts by weight of the liquid crystalline compound in the coating liquid. It can be used in an amount of 5 to 15 parts by weight.

  As the chiral agent, a compound that exhibits a cholesteric phase alone or an optically active organic compound that does not exhibit a cholesteric phase alone but exhibits a cholesteric phase when mixed with the liquid crystal compound can be used. As the optically active chiral agent, nematic liquid crystal analogs such as optically active ester derivatives, optically active cyanobiphenyl derivatives, and optically active bisphenol derivatives can be used. The chiral agent can be used in an amount of 1 to 40 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the liquid crystalline compound in the coating liquid.

  If necessary, an appropriate amount of a thermal polymerization initiator, a resin, a polyfunctional monomer and / or oligomer, a surfactant, a polymerization inhibitor, a storage stabilizer, an adhesion improver, and the like can be added to the coating liquid. . These may be the same as the compounds used for the black colored composition described above.

  Application of the coating liquid includes, for example, spin coating, slit coating, letterpress printing, screen printing, planographic printing, reversal printing, gravure printing and the like, a method combining these printing methods with an offset method, ink jet Method, or bar coat method.

  The liquid crystal material layer is formed as a continuous film having a uniform thickness, for example. According to the method described above, as long as the coated surface is sufficiently flat, the liquid crystal material layer can be formed as a continuous film having a uniform thickness.

  Prior to the application of the coating solution, the surface of the color filter layer 220 may be subjected to an alignment treatment. Alternatively, an alignment film that regulates the alignment of the liquid crystal compound may be formed on the color filter layer 220 prior to application of the coating liquid. This alignment film is obtained, for example, by forming a transparent resin layer such as polyimide on the color filter layer 220 and subjecting this transparent resin layer to an alignment treatment such as rubbing. This alignment film may be formed using a photo-alignment technique.

  Next, an exposure process is performed. That is, light is irradiated to a predetermined region of the liquid crystal material layer. For example, light is irradiated to regions corresponding to the regions 230Ra, 230Rb, and 230Rc in the liquid crystal material layer, and light is not irradiated to regions corresponding to the region 230T in the liquid crystal material layer. As a result, polymerization or cross-linking of the thermotropic liquid crystal compound is caused while maintaining the alignment structure formed by the mesogen at the portion of the liquid crystal material layer irradiated with light.

  As the light, it is preferable to use light having a short wavelength component in the ultraviolet light. Thereby, the width of the boundary 230H of the solidified liquid crystal layer 230 can be reduced. In principle, light with many short wavelength components is preferable. However, in order to obtain the solidified liquid crystal layer 230 of the present invention in which the width of the boundary 230H is 8 μm or less, the light has an irradiance Es and a wavelength of 200 nm to 319 nm. If the ratio Es / Em of the irradiance Em of 320 nm to 370 nm satisfies the condition of 5 or more, it is sufficient for practical use. In addition, since the component exceeding the wavelength of 370 nm in the light hardly causes polymerization or cross-linking of the liquid crystal compound in the liquid crystal material layer of the present invention, the magnitude of the illuminance hardly affects the quality of the obtained solidified liquid crystal layer 230. Does not affect.

  In the exposure step, the light irradiation may be performed so as to satisfy different conditions in a plurality of regions of the liquid crystal material layer. The different conditions indicate that the exposure time, illuminance, bright line, etc., or a combination thereof is different. Usually, the exposure process is performed so that each region has different irradiation energy, that is, different exposure amount, but depending on the material, a reciprocity failure characteristic is observed. In that case, it is not always necessary to vary the exposure amount for each region. For example, a certain region may be exposed for a short time with high illuminance, and another region may be exposed for a long time with low illuminance. As a result, the exposure amount (illuminance × exposure time) in both regions may be the same. However, in any region, it is preferable to irradiate light that satisfies the above-mentioned irradiance ratio Es / Em of 5 or more.

  Hereinafter, a case where the exposure amount varies depending on the region will be described as an example.

  For example, the region corresponding to the region 230Ra in the liquid crystal material layer is irradiated with light with the maximum exposure amount. The region corresponding to the region 230Rb in the liquid crystal material layer is irradiated with light with a smaller exposure amount than the region corresponding to the region 230Ra in the liquid crystal material layer. The region corresponding to the region 230Rc in the liquid crystal material layer is irradiated with light with a smaller exposure amount than the region corresponding to the region 230Rc in the liquid crystal material layer. For example, the region corresponding to the region 230T in the liquid crystal material layer is not irradiated with light. As a result, polymerization or cross-linking of the thermotropic liquid crystal compound is caused while maintaining the alignment structure formed by the mesogen at the portion of the liquid crystal material layer irradiated with light.

  In the polymerization or cross-linked product of the thermotropic liquid crystal compound, the mesogen is immobilized. In the region where the exposure amount is the maximum, the content of the thermotropic liquid crystal compound is the highest, or the content of the crosslinked product is the highest, and the content of the unpolymerized and uncrosslinked thermotropic liquid crystal compounds is the lowest. As the exposure amount decreases, the content of the polymerized or crosslinked product decreases, and the content of the unpolymerized and uncrosslinked thermotropic liquid crystal compounds increases.

  Accordingly, mesogens are immobilized at a higher rate in regions where the exposure amount is larger, and mesogens are immobilized at a lower rate in regions where the exposure amount is smaller. And in the area | region where an exposure amount is zero, a mesogen is not fix | immobilized.

  The exposure step may be performed by any method as long as the above-described non-uniform polymerization or crosslinking can be caused. For example, in this exposure step, exposure using a photomask may be performed a plurality of times. Alternatively, in this exposure step, exposure using a halftone mask, a gray tone mask, or a wavelength limiting mask may be performed. Alternatively, instead of using a photomask, the light beam may be scanned on the liquid crystal material layer. Furthermore, these may be combined.

  Typically, a proximity exposure method in which a mask such as the above-described photomask, halftone mask, graytone mask, or wavelength limiting mask is disposed in the vicinity of the liquid crystal material layer and irradiated with parallel light is used.

  After the exposure process is completed, a development process is performed. That is, the liquid crystal material layer is heated to a temperature equal to or higher than the phase transition temperature at which the thermotropic liquid crystal compound changes from the liquid crystal phase to the isotropic phase. The mesogen of the thermotropic liquid crystal compound which is an unreacted compound is not immobilized. Therefore, when the liquid crystal material layer is heated to a temperature higher than the phase transition temperature, the degree of alignment of the unreacted compound mesogen decreases. For example, the unreacted compound mesogen changes from a liquid crystal phase to an isotropic phase. On the other hand, the mesogen is immobilized in the polymerized or crosslinked product of the thermotropic liquid crystal compound.

  Therefore, the region that has not been irradiated with light changes to an isotropic phase, and a pattern with an anisotropic phase region and an isotropic phase region where the orientation is fixed, that is, the orientation structure remains, appears. In the exposure step, when light is irradiated with a different exposure amount for each region, the degree of orientation decreases depending on the content of the unpolymerized and uncrosslinked thermotropic liquid crystal compounds. For example, compared with the region corresponding to the region 230Ra, the region corresponding to the region 230Rb has a lower degree of orientation, and the region corresponding to the region 230Rc has a lower degree of orientation. In the region corresponding to the region 230T, for example, the orientation disappears.

  Thereafter, a fixing step is performed. That is, the unreacted compound is polymerized and / or crosslinked while reducing the degree of orientation of the unreacted compound mesogen.

  The fixing process is performed, for example, by irradiating the entire substrate with light. That is, almost all of the unreacted compound undergoes polymerization and / or crosslinking reaction while maintaining the liquid crystal material layer at a temperature higher than the phase transition temperature at which the thermotropic liquid crystal compound changes from the isotropic phase to the liquid crystal phase. The entire liquid crystal material layer is irradiated with light with a sufficient exposure amount. Thereby, polymerization or crosslinking of the unreacted compound is caused in the liquid crystal material layer, and the mesogen is immobilized while the degree of alignment is lost or reduced. The solidified liquid crystal layer 230 is obtained as described above.

  A certain liquid crystal compound has a lower first phase transition temperature that changes from an isotropic phase to a liquid crystal phase than a second phase transition temperature that changes from a liquid crystal phase to an isotropic phase. Therefore, in a specific case, the temperature of the liquid crystal material layer in the fixing step may be lower than the heating temperature in the developing step. However, normally, from the viewpoint of simplicity, the temperature of the liquid crystal material layer in the fixing step is set to be equal to or higher than the first phase transition temperature.

  In the exposure in the fixing step, the type of light is not limited as long as it can induce polymerization and / or crosslinking reaction of the unreacted compound.

  The fixing step may be performed by other methods.

  For example, when an unreacted compound, that is, a thermotropic liquid crystal compound is a material that polymerizes and / or crosslinks by heating to a polymerization and / or crosslinking temperature higher than the first phase transition temperature, heating is performed instead of light irradiation. May be. Specifically, instead of irradiating light, the liquid crystal material layer is heated to a polymerization and / or crosslinking temperature or higher to polymerize and / or crosslink the unreacted compound. Thereby, the solidified liquid crystal layer 230 is obtained. The heating temperature in the development step is, for example, not lower than the first phase transition temperature and lower than the polymerization and / or crosslinking temperature.

  Alternatively, light irradiation and heating may be sequentially performed in the fixing step. When light and heat are combined in this way, polymerization and / or crosslinking of the unreacted compound can proceed more reliably. Therefore, a stronger solidified liquid crystal layer 230 can be obtained.

  When the unreacted compound is a material that polymerizes and / or crosslinks by heating to a certain temperature, the heating temperature in the development step may be higher than the temperature at which it polymerizes and / or crosslinks. That is, the developing process and the fixing process may be performed simultaneously. However, in this case, a decrease in the degree of orientation and polymerization and / or crosslinking proceed simultaneously. Therefore, the influence of the manufacturing conditions on the optical characteristics of the solidified liquid crystal layer 230 is relatively large.

  In the retardation substrate of the present invention, a retardation pattern is formed without a wet process. In order to form a pattern by a wet process, a liquid having an ability to dissolve the liquid crystal material layer, such as a solvent or an alkaline aqueous solution, is used. For example, a pattern is formed by removing uncured portions by immersing the liquid in the liquid crystal material layer or spraying the liquid on the liquid crystal material layer by spraying or the like.

  However, it is difficult to strictly control the conditions of these wet processes, and the influence of these conditions on the optical properties of the final product is extremely large. Therefore, according to the method including the wet process, the deviation of the optical characteristic from the target value is likely to occur.

  On the other hand, in the method of the present invention, the wet process is not performed after the exposure step. Therefore, it is possible to prevent the refractive index anisotropy from deviating from the target value due to the wet process.

  The refractive index anisotropy and the exposure amount in the exposure step are not necessarily in a proportional relationship, but the reproducibility of the refractive index anisotropy is high under the condition that the material and the exposure amount are constant. Therefore, it is easy to find the conditions necessary to achieve a certain refractive index anisotropy, for example, the exposure amount, and it is also easy to perform stable production.

  Hereinafter, although the specific example of this invention is shown, this invention is not limited to these. Since the material used in the present invention is extremely sensitive to light, it is necessary to prevent exposure to unnecessary light such as natural light, and all operations are performed under a yellow or red light. In the examples and comparative examples, “parts” means “parts by weight”.

  An alignment film material (“SE-1410” manufactured by Nissan Chemical Industries, Ltd.) is applied on a glass substrate with a spin coater so that the dry film thickness is 0.1 μm, and is heated and dried at 90 ° C. for 1 minute on a hot plate. Then, it was baked at 230 ° C. for 40 minutes in a clean oven. Subsequently, a rubbing process was performed on the substrate in a certain direction to obtain a substrate having orientation ability.

  A mixture having the following composition was stirred and mixed so as to be uniform, and filtered through a 0.6 μm filter to obtain a coating solution.

Horizontally polymerizable liquid crystal 19.76 parts (“UCL-017” manufactured by DIC Corporation)
0.24 parts of photopolymerization initiator (“Irgacure OXE01” manufactured by Ciba Specialty Chemicals Co., Ltd.)
Surfactant 1.00 parts ("BYK330" 1% cyclohexanone solution manufactured by Big Chemie)
Cyclohexanone 63.20 parts 2-acetoxy-1-methoxypropane 15.80 parts (Example 1)
The substrate having the above-mentioned alignment ability was placed on a spin coater, and the coating liquid prepared earlier was dropped while being rotated at about 350 revolutions / minute, and coating was performed.

Next, using a photomask, a part of the substrate was irradiated with light for 8 seconds. An ultra-high pressure mercury lamp was used as the light source, and a 200-300 nm band pass filter was inserted between the light source and the substrate. Irradiance Es is 38.1mW / cm ² in the wavelength 200Nm～319nm, irradiance Em wavelength 320nm~370nm is 0.4 mW / cm ^2, irradiance El wavelength 371nm~450nm was 1.6 mW / cm ² . The characteristics of the irradiated light are as shown in Table 1 below. FIG. 8 shows emission lines of irradiated light.

  The exposed substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to produce a substrate with a solidified liquid crystal layer (retardation substrate).

  When the phase difference of the obtained retardation substrate was measured, the phase difference of the region irradiated with light (anisotropic phase part) was 217 nm, and the phase difference of the region not irradiated with light (isotropic phase part) was 0 nm. there were. Moreover, the width | variety of the area | region (boundary) whose phase difference formed in the middle of both area | regions is 22 nm or more and 195 nm or less was 5.6 micrometers.

(Example 2)
The substrate having the above-mentioned alignment ability was placed on a spin coater, and the coating liquid prepared earlier was dropped while being rotated at about 390 rpm, and coating was performed.

Next, using a photomask, a part of the substrate was irradiated with light for 8 seconds. An ultrahigh pressure mercury lamp was used as the light source, and a 312 nm bandpass filter was inserted between the light source and the substrate. Irradiance Es is 15.9mW / cm ² in the wavelength 200Nm～319nm, irradiance Em wavelength 320nm~370nm is 3.0 mW / cm ^2, irradiance El wavelength 371nm~450nm was 1.0 mW / cm ² . The characteristics of the irradiated light are as shown in Table 2 below. FIG. 9 shows emission lines of irradiated light.

  The exposed substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to produce a substrate with a solidified liquid crystal layer (retardation substrate).

  When the phase difference of the obtained retardation substrate was measured, the phase difference of the region irradiated with light (anisotropic phase part) was 228 nm, and the phase difference of the region not irradiated with light (isotropic phase part) was 0 nm. there were. Moreover, the width | variety of the area | region (boundary) whose phase difference formed in the middle of both area | regions is 23 nm or more and 205 nm or less was 7.0 micrometers.

(Example 3)
The substrate having the above-mentioned alignment ability was placed on a spin coater, and the coating liquid prepared earlier was dropped while being rotated at about 360 rpm, and coating was performed.

Next, using a photomask, a part of the substrate was irradiated with light for 8 seconds. An ultra-high pressure mercury lamp was used as the light source, and a 350 nm long wavelength cut filter was inserted between the light source and the substrate. Irradiance Es is 50.6mW / cm ² in the wavelength 200Nm～319nm, irradiance Em wavelength 320nm~370nm is 0.4 mW / cm ^2, irradiance El wavelength 371nm~450nm was 9.3mW / cm ² . The characteristics of the irradiated light are as shown in Table 3 below. FIG. 10 shows emission lines of irradiated light.

  The exposed substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to produce a substrate with a solidified liquid crystal layer (retardation substrate).

  When the phase difference of the obtained retardation substrate was measured, the phase difference of the region irradiated with light (anisotropic phase portion) was 220 nm, and the phase difference of the region not irradiated with light (isotropic phase portion) was 0 nm. there were. Moreover, the width | variety of the area | region (boundary) whose phase difference formed in the middle of both area | regions is 22 nm or more and 198 nm or less was 5.6 micrometers.

(Comparative Example 1)
The substrate having the above-mentioned alignment ability was placed on a spin coater, and the coating liquid prepared earlier was dropped while applying the coating at a speed of about 440 rpm, and coating was performed.

Next, using a photomask, a part of the substrate was irradiated with light for 8 seconds. An ultra-high pressure mercury lamp was used as the light source, and no wavelength cut filter was used. Irradiance Es at a wavelength of 200 nm to 319 nm was 80.9 mW / cm ² , Irradiance Em at a wavelength of 320 nm to 370 nm was 34.6 mW / cm ² , and Irradiance El at a wavelength of 371 nm to 450 nm was 22.1 mW / cm ² . . The characteristics of the irradiated light are as shown in Table 4 below. FIG. 11 shows emission lines of irradiated light.

  The exposed substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to produce a substrate with a solidified liquid crystal layer (retardation substrate).

  When the phase difference of the obtained retardation substrate was measured, the phase difference of the region irradiated with light (anisotropic phase portion) was 223 nm, and the phase difference of the region not irradiated with light (isotropic phase portion) was 0 nm. there were. Moreover, the width | variety of the area | region (boundary) whose phase difference formed in the middle of both area | regions is 22 nm or more and 201 nm or less was 9.1 micrometers.

(Comparative Example 2)
The substrate having the above-mentioned alignment ability was placed on a spin coater, and the coating liquid prepared earlier was dropped while being rotated at about 400 revolutions / minute, and coating was performed.

Next, using a photomask, a part of the substrate was irradiated with light for 8 seconds. An ultra-high pressure mercury lamp was used as the light source, and a 350 nm short wavelength cut filter was inserted between the light source and the substrate. Irradiance Es at a wavelength of 200 nm to 319 nm was 0.0 mW / cm ² , Irradiance Em at a wavelength of 320 nm to 370 nm was 19.2 mW / cm ² , and Irradiance El at a wavelength of 371 nm to 450 nm was 15.6 mW / cm ² . . The characteristics of the irradiated light are as shown in Table 5 below. FIG. 12 shows emission lines of irradiated light.

  The exposed substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to produce a substrate with a solidified liquid crystal layer (retardation substrate).

  When the phase difference of the obtained retardation substrate was measured, the phase difference of the region irradiated with light (anisotropic phase part) was 230 nm, and the phase difference of the region not irradiated with light (isotropic phase part) was 0 nm. there were. Moreover, the width | variety of the area | region (boundary) whose phase difference formed in the middle of both area | regions is 23 nm or more and 207 nm or less was 9.1 micrometers.

(Comparative Example 3)
The substrate having the above-mentioned alignment ability was placed on a spin coater, and the coating liquid prepared earlier was dropped while being rotated at about 390 rpm, and coating was performed.

Next, using a photomask, a part of the substrate was irradiated with light for 8 seconds. An ultra-high pressure mercury lamp was used as the light source, and a 365 nm band pass filter was inserted between the light source and the substrate. Irradiance Es at a wavelength of 200 nm to 319 nm was 7.4 mW / cm ² , Irradiance Em at a wavelength of 320 nm to 370 nm was 24.2 mW / cm ² , and Irradiance El at a wavelength of 371 nm to 450 nm was 5.2 mW / cm ² . . The characteristics of the irradiated light are as shown in Table 6 below. FIG. 13 shows emission lines of irradiated light.

  The exposed substrate was placed in a clean oven and baked at 230 ° C. for 40 minutes to produce a substrate with a solidified liquid crystal layer (retardation substrate).

  When the phase difference of the obtained retardation substrate was measured, the phase difference of the region irradiated with light (anisotropic phase part) was 230 nm, and the phase difference of the region not irradiated with light (isotropic phase part) was 0 nm. there were. Moreover, the width | variety of the area | region (boundary) whose phase difference formed in the middle of both area | regions is 23 nm or more and 207 nm or less was 8.4 micrometers.

Table 7 summarizes the phase difference and boundary width of the solidified liquid crystal layer in each phase difference substrate together with the characteristics of the irradiation light used during exposure.

  As shown in Table 7, Es / Em (Es is the irradiance of light having a wavelength of 200 nm to 319 nm and Em is the irradiance of light having a wavelength of 320 nm to 370 nm) is irradiated with light of 5 or more. By doing so, the width of the boundary between the anisotropic phase portion and the isotropic phase portion can be suppressed to less than 8 μm.

Further benefits and variations are readily apparent to those skilled in the art. Therefore, the invention in its broader aspects should not be limited to the specific descriptions and representative embodiments described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the generic concept of the invention as defined by the appended claims and their equivalents.
The invention described in the scope of claims of the present application will be appended below.
[1] a light-transmitting planar body;
A solidified liquid crystal layer that is supported by the planar body and formed as a continuous film made of the same material;
The solidified liquid crystal layer is
Including an anisotropic phase portion having refractive index anisotropy and an isotropic phase portion having no refractive index anisotropy,
A width of a boundary between the anisotropic phase portion and the isotropic phase portion is less than 8 μm.
[2] The unit according to [1], wherein the anisotropic phase portion in the solidified liquid crystal layer has two or more regions having different birefringence due to different degrees of orientation. Phase difference board.
[3] The retardation substrate according to [1] or [2], wherein the thickness of the solidified liquid crystal layer is uniform.
[4] The retardation substrate according to any one of [1] to [3], wherein the solidified liquid crystal layer is formed by polymerizing and / or crosslinking a thermotropic liquid crystal compound.
[5] The phase difference according to any one of [2] to [4], wherein a width of a boundary between the two or more regions in the anisotropic phase portion of the solidified liquid crystal layer is less than 8 μm. substrate.
[6] The anisotropic phase portion in the solidified liquid crystal layer includes an a1 region, an a2 region, and an a3 region, and the a1 region has a higher birefringence than the a2 region, The retardation substrate according to any one of [2] to [5], wherein the a2 region has a larger birefringence than the a3 region.
[7] It further includes a color filter layer interposed between the planar body and the solidified liquid crystal layer, or facing the planar body via the solidified liquid crystal layer,
The color filter layer has two or more colored pixels having different wavelengths of transmitted light, and the colored pixels are each composed of a reflective display region and a transmissive display region,
The reflective display region of the colored pixel faces the anisotropic phase portion of the solidified liquid crystal layer to form a reflective display portion, and the transmissive display region of the colored pixel is the transmissive display region of the solidified liquid crystal layer. The retardation substrate according to any one of [1] to [6], wherein the transmissive display unit is configured to face the isotropic phase unit.
[8] In the reflective display unit, the color filter layer includes a red pixel, a green pixel, and a blue pixel, and includes the anisotropic phase portion of the solidified liquid crystal layer.
The red pixel faces the a1 region,
The green pixel faces the a2 region,
The blue pixel faces the a3 region
The retardation substrate as described in [7], wherein
[9] The color filter layer further includes a black separation wall,
The black separation wall separates the colored pixels of the color filter layer, separates the transmissive display area and the reflective display area of each colored pixel,
The phase difference substrate according to [7] or [8], wherein the boundary in the solidified liquid crystal layer faces at least a part of the black separation wall.
[10] A transflective liquid crystal display device comprising the retardation substrate according to any one of [1] to [9].
[11] including forming a solidified liquid crystal layer on a light-transmitting planar body directly or via another layer,
A film forming step of forming a liquid crystal material layer on the planar body, which includes a photopolymerizable or photocrosslinkable thermotropic liquid crystal compound, and a mesogen of the thermotropic liquid crystal compound forms an alignment structure;
Light having Es / Em (Es is the irradiance of light having a wavelength of 200 nm to 319 nm and Em is the irradiance of light having a wavelength of 320 nm to 370 nm) in a part of the liquid crystal material layer. A first region containing a reaction product in which the thermotropic liquid crystal compound is polymerized or cross-linked in the liquid crystal material layer, and the unreacted thermotropic liquid crystal compound not containing the reaction product. An exposure step for forming a second region including:
Thereafter, the development step of heating the liquid crystal material layer to a temperature equal to or higher than a phase transition temperature at which the thermotropic liquid crystal compound changes from a liquid crystal phase to an isotropic phase to substantially lose the orientation of the mesogen in the second region. When,
A fixing step of polymerizing and / or cross-linking the unreacted thermotropic liquid crystal compound while substantially losing the orientation of the mesogen in the second region.
A method of manufacturing a retardation substrate, comprising:
[12] forming a solidified liquid crystal layer on a light-transmitting planar body directly or via another layer, and forming the solidified liquid crystal layer includes:
A film forming step of forming a liquid crystal material layer on the planar body, which includes a photopolymerizable or photocrosslinkable thermotropic liquid crystal compound, and a mesogen of the thermotropic liquid crystal compound forms an alignment structure;
Es / Em (Es is the irradiance of light having a wavelength of 200 nm or more and 319 nm or less, and Em is the irradiance of light having a wavelength of 320 nm or more and 370 nm or less in at least two regions of the liquid crystal material layer while leaving an unexposed portion. ) Is irradiated with 5 or more light under different conditions, and in the liquid crystal material layer, a first region containing a reaction product in which the thermotropic liquid crystal compound is polymerized or crosslinked, and an unreacted product not containing the reaction product Exposure that forms a second region containing the thermotropic liquid crystal compound, and a third region containing the reaction product and the unreacted thermotropic liquid crystal compound, wherein the content of the reaction product is lower than the first region. Process,
Thereafter, the liquid crystal material layer is heated to a temperature equal to or higher than a phase transition temperature at which the thermotropic liquid crystal compound changes from a liquid crystal phase to an isotropic phase to reduce the degree of orientation of the mesogens in at least the three regions, A development step that substantially loses the orientation of the mesogens in the second region;
A fixing step of polymerizing and / or crosslinking the unreacted thermotropic liquid crystal compound while reducing the degree of orientation of the mesogen in the third region and losing the orientation of the mesogen in the second region;
A method of manufacturing a retardation substrate, comprising:
[13] The method according to [11] or [12], wherein in the fixing step, the polymerization and / or crosslinking of the unreacted thermotropic liquid crystal compound is induced by light irradiation.
[14] The thermotropic liquid crystal compound is a material that polymerizes and / or crosslinks by heating to a polymerization and / or crosslinking temperature higher than the phase transition temperature,
In the developing step, by heating the liquid crystal material layer to a temperature lower than the polymerization and / or crosslinking temperature, the orientation of the mesogen is eliminated and / or the degree of orientation is reduced,
In the fixing step, the unpolymerized and / or uncrosslinked thermotropic liquid crystal compound is polymerized and / or crosslinked by heating the liquid crystal material layer to a temperature equal to or higher than the polymerization and / or crosslinking temperature. The manufacturing method according to any one of [11] to [13].
[15] The method according to any one of [11] to [14], wherein the liquid crystal material layer is formed as a continuous film having a uniform thickness.
[16] The method according to any one of [11] to [15], further including a step of forming a color filter layer directly on the planar body or via another layer before forming the solidified liquid crystal layer. The manufacturing method in any one.
[17] The manufacturing method according to any one of [11] to [15], further including a step of forming a color filter layer directly or via another layer on the solidified liquid crystal layer. .
[18] The method further includes the step of forming a black separation wall so as to include a region facing the boundary region of the solidified liquid crystal layer before forming the color filter layer. Or the manufacturing method as described in [17].

DESCRIPTION OF SYMBOLS 10 ... Array substrate; 20 ... Opposite substrate; 30 ... Liquid crystal layer; 110 ... Planar body 150R ... Reflective electrode; 150T ... Transparent electrode; 160 ... Alignment film; 220b ... second colored pixel 220c ... third colored pixel; 220a _R ... first reflective display area 220a _T ... first transmissive display area; 220b _R ... second reflective display area 220b _T ... second transmissive display 220c _R ... third reflective display area 220c _T ... third transmissive display area; 230 ... solidified liquid crystal layer; 230Ra ... area 230Rb ... area; 230Rc ... area; 230T ... area; 230H ... boundary 250 ... counter electrode 260 ... Alignment film; 270 ... Black separation wall.

Claims (8)

A light-transmitting planar body, and a solidified liquid crystal layer supported by the planar body and formed as a continuous film made of the same material, the solidified liquid crystal layer having anisotropic refractive index A phase difference substrate including an isotropic phase portion having no refractive index anisotropy, and a width of a boundary between the anisotropic phase portion and the isotropic phase portion is less than 8 μm,
Forming a solidified liquid crystal layer on a light-transmitting planar body directly or via another layer, and forming the solidified liquid crystal layer includes:
A film forming step of forming a liquid crystal material layer on the planar body, which includes a photopolymerizable or photocrosslinkable thermotropic liquid crystal compound, and a mesogen of the thermotropic liquid crystal compound forms an alignment structure;
Light having Es / Em (Es is the irradiance of light having a wavelength of 200 nm to 319 nm and Em is the irradiance of light having a wavelength of 320 nm to 370 nm) in a part of the liquid crystal material layer. A first region containing a reaction product in which the thermotropic liquid crystal compound is polymerized or cross-linked in the liquid crystal material layer, and the unreacted thermotropic liquid crystal compound not containing the reaction product. An exposure step for forming a second region including:
Thereafter, the development step of heating the liquid crystal material layer to a temperature equal to or higher than a phase transition temperature at which the thermotropic liquid crystal compound changes from a liquid crystal phase to an isotropic phase to substantially lose the orientation of the mesogen in the second region. When,
And a fixing step of polymerizing and / or cross-linking the unreacted thermotropic liquid crystal compound while substantially losing the orientation of the mesogen in the second region. A light-transmitting planar body, and a solidified liquid crystal layer supported by the planar body and formed as a continuous film made of the same material, the solidified liquid crystal layer having anisotropic refractive index A phase difference substrate including an isotropic phase portion having no refractive index anisotropy, and a width of a boundary between the anisotropic phase portion and the isotropic phase portion is less than 8 μm,
Forming a solidified liquid crystal layer on a light-transmitting planar body directly or via another layer, and forming the solidified liquid crystal layer includes:
A film forming step of forming a liquid crystal material layer on the planar body, which includes a photopolymerizable or photocrosslinkable thermotropic liquid crystal compound, and a mesogen of the thermotropic liquid crystal compound forms an alignment structure;
Es / Em (Es is the irradiance of light having a wavelength of 200 nm or more and 319 nm or less, and Em is the irradiance of light having a wavelength of 320 nm or more and 370 nm or less in at least two regions of the liquid crystal material layer while leaving an unexposed portion. ) Is irradiated with 5 or more light under different conditions, and in the liquid crystal material layer, a first region containing a reaction product in which the thermotropic liquid crystal compound is polymerized or crosslinked, and an unreacted product not containing the reaction product Exposure that forms a second region containing the thermotropic liquid crystal compound, and a third region containing the reaction product and the unreacted thermotropic liquid crystal compound, wherein the content of the reaction product is lower than the first region. Process,
Thereafter, the liquid crystal material layer is heated to a temperature equal to or higher than a phase transition temperature at which the thermotropic liquid crystal compound changes from a liquid crystal phase to an isotropic phase to reduce the degree of orientation of the mesogens in at least the three regions, A development step that substantially loses the orientation of the mesogens in the second region;
A fixing step of polymerizing and / or crosslinking the unreacted thermotropic liquid crystal compound while reducing the degree of orientation of the mesogen in the third region and losing the orientation of the mesogen in the second region. A method for producing a retardation substrate, comprising: The method according to claim 1 or 2 , wherein in the fixing step, the polymerization and / or crosslinking of the unreacted thermotropic liquid crystal compound is induced by light irradiation. The thermotropic liquid crystal compound is a material that polymerizes and / or crosslinks by heating to a polymerization and / or crosslinking temperature higher than the phase transition temperature,
In the developing step, by heating the liquid crystal material layer to a temperature lower than the polymerization and / or crosslinking temperature, the orientation of the mesogen is eliminated and / or the degree of orientation is reduced,
In the fixing step, the unpolymerized and / or uncrosslinked thermotropic liquid crystal compound is polymerized and / or crosslinked by heating the liquid crystal material layer to a temperature equal to or higher than the polymerization and / or crosslinking temperature. The manufacturing method according to any one of claims 1 to 3 . The process according to any one of claims 1 to 4, characterized in that to form the liquid crystal material layer as a continuous film of uniform thickness. Before forming the solidified liquid crystal layer, in any one of claims 1 to 5, further comprising a step of forming a color filter layer directly or via another layer on the planar body The manufacturing method as described. On the solidified liquid crystal layer, the manufacturing method according to any one of claims 1 to 5 directly or via another layer, characterized in that it further comprises a step of forming a color filter layer. Before forming the color filter layer, so as to include a region facing the region of the boundary of the solidified liquid crystal layer, in claim 6 or 7, further comprising a step of forming a black Hanarega wall The manufacturing method as described.

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