JP2006079011A - Color filter structure and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter structure that realizes high color reproducibility and contrast.
A color filter structure used in a liquid crystal display device, the color filter formed as an aggregate of fine regions corresponding to red, green and blue pixels colored with a pigment, and a visible wavelength region A white color based on the chromaticity of the red, green, and blue fine regions of the color filter, which is composed of a high-contrast filter in which a dye having an absorption peak is monodispersed in a resin, and is measured using a CIE standard C light source The display chromaticity is x, y ≦ 0.29 at x, y in the CIE XYZ color system, and the chromaticity of the high contrast filter measured using the C light source is 0.31 ≦ at x, y. x, y ≦ 0.45 and the chromaticity as a color filter structure measured using the C light source is 0.29 ≦ x, y ≦ 0.3 in x and y. A color filter structure, characterized in that it.
[Selection figure] None

Description

  The present invention relates to a color filter structure and a liquid crystal display device that realize high color reproducibility and contrast.

  Color liquid crystal display devices (color LCDs) are widely used against the background of lower prices and larger liquid crystal display panels. In recent years, display image quality has become a major factor in product differentiation. There are various indexes of image quality, but it is desired that the contrast is high and the color reproduction range is high.

  A liquid crystal display device is a light source (a liquid crystal cell layer sandwiched between two polarizing films) that passes through the first polarizing film by adjusting the voltage applied to the electrodes provided between the layers for each pixel. This is a device that performs display by controlling the degree of polarization of light from a backlight unit or the like and controlling the amount of light passing through the second polarizing film.

When performing color display with a liquid crystal display device, a color filter that is an aggregate of fine areas of red, blue, and green is usually provided between the liquid crystal cell layer and the second polarizing film, and blue, red, and green One pixel is displayed using at least one region.
Therefore, the emission spectrum of the light source and the spectral characteristics of the color filter are major factors that determine the color purity and color reproduction range of the liquid crystal display device.
At present, image quality is improved mainly by improving the spectral characteristics of the color filter.

  As a method for producing a color filter, methods such as a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method are known, but the pigment dispersion method is mainly used at present from the viewpoint of durability. However, since the pigment is a crystal particle of about 10 to 1000 nm, the reflection (that is, scattering) on the surface causes a change in the polarization direction that is considered to be caused by the birefringence of the crystal particle, resulting in light scattering. In order to deteriorate the polarization characteristics (the degree of alignment of the vibration direction of light), the contrast is lowered such that light that should be blocked by the second polarizing film leaks. In addition, the particles are essentially inferior in transparency (transmittance) compared to dyes that exhibit color only by molecular absorption. Any of these problems is a phenomenon caused by scattering from the pigment. In general, the smaller the particle diameter, the better the characteristics. However, the difficulty of atomization differs depending on the pigment type. In particular, dioxazine violet, which is a purple pigment used for blue pixels, is difficult to atomize, which is a cause of hindering high contrast.

As the backlight, generally, a cold cathode tube having emission wavelengths in the red, green, and blue wavelength regions is used as a light source, and light emitted from the cold cathode tube is converted into a white surface light source by a light guide plate. Among the light emitters of cold-cathode tubes, Y ₂ O ₃ : Eu phosphors as red emitters, LaPO ₄ : Ce, Tb phosphors as green emitters, and BaMgAl ₁₀ O ₁₇ : Eu as blue emitters. A phosphor based on Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu is generally used. A fluorescent lamp in which an electrode is mounted in an envelope provided with a phosphor film in which these phosphors are mixed at an appropriate blending ratio in consideration of white balance and a rare gas is enclosed is used as a light source for backlight.

  Some backlights use a substrate provided with a phosphor layer and a cathode tube or LED that emits ultraviolet light, blue light, or deep blue light, and the phosphor is excited by light from these to be used as a white surface light source. . There is also a method of combining three color LEDs that emit light in the red, green, and blue wavelength regions.

JP 2004-133208 A

  In order to improve transparency in a color filter using pigments, it has been found that pigment atomization is effective, and various pigment atomization methods and dispersion methods of atomized pigments have been proposed. However, there is a problem that the smaller the particle size, the more the pigment surface area increases, the coating solution becomes unstable, and the control of coating properties becomes difficult. In addition, since pigments are inherently microcrystalline, excessive atomization leads to collapse of the crystal system and changes the color tone. For these reasons, there was a natural limit to atomization.

  Since it is necessary to use a lot of pigments to reproduce colors with high density, when using the same color material, the color reproduction range (reproduction ability from light to dark colors) and brightness (high transmittance) Is in a trade-off relationship. Accordingly, there is a strong demand for a technique for improving the brightness while maintaining the color reproduction range (or expanding the color reproduction range while maintaining the brightness).

  In addition, as a light source of the liquid crystal display device, a three-wavelength tube using a phosphor having emission peaks in the R, G, B wavelength regions is usually used. However, these phosphors have weak emission peaks in wavelength regions other than R, G, and B as sub-emission peaks, so that the color purity is deteriorated.

  Since deterioration in color purity hinders the expansion of the color reproduction range of the liquid crystal display element, it is conceivable to add a dye having a characteristic of absorbing a wavelength region corresponding to the sub-emission peak to the color filter. However, the absorption peak of the existing dye always has a finite width, and is usually about 60 nm in half width. Since the sub-emission peak has a wavelength close to the main emission peak, even if there is a dye having the maximum absorption wavelength λmax in the sub-emission peak wavelength, the base of the absorption spectrum is affected by the main emission peak wavelength, and only the sub-emission part is It is impossible to lose. For this reason, if the amount of the dye is increased in order to reduce the light at the sub-emission peak as much as possible, the overall image becomes dark and has a low contrast.

  In particular, the absorption spectrum of Pigment Green (P.G.) 36, Pigment Blue (P.B.) 15: 6, which is commonly used to form the green and blue regions of the color filter, is broad. This problem is remarkable. In addition, the pigment concentration in each pixel region of the color filter is increased, so that the performance as a photolithography material is deteriorated (for example, the development time is increased, the pattern shape is difficult to control, the yield is decreased, etc.). was there.

  A technique for cutting only the sub-emission peak wavelength of a phosphor using an optical diffraction grating without using a dye has also been proposed, but there is a problem in terms of cost because it is necessary to stack layers having different refractive indexes. .

In view of such prior art, the applicant first uses a light control film that further adjusts the transmitted light spectrum from the color filter, and obtains a desired emission spectrum by combining the color filter and the light control film. (Patent Document 1).
An object of the present invention is to provide a color filter for realizing a color liquid crystal display device with good color reproducibility and high contrast based on the idea of Patent Document 1.

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that the function of the color filter is to use a layer using a pigment (a layer corresponding to a normal color filter) and a layer using a dye other than the pigment (high Realized by a structure consisting of a combination with (contrast filter layer), specifically, by controlling the spectral characteristics (absorption characteristics) of individual layers so as to realize the spectral characteristics required for color filters. It has been found that reproducibility and contrast can be realized simultaneously.

  The high contrast filter can be manufactured separately from the color filter, so that the color filter can be manufactured without being exposed to the severe high temperatures experienced in the manufacturing process. For this reason, the heat resistance condition in selecting a dye is greatly relaxed, and a dye other than the pigment such as a dye can be used. Therefore, by supplementing the broad absorption spectrum, which is a defect of the pigment, with the sharp absorption spectrum, which is a characteristic of the dye, it is possible to realize a spectral spectrum that cannot be achieved by a color filter using only the pigment as a whole. Furthermore, since the amount of pigment used can be reduced, the light transmittance of the color filter can also be improved, and a liquid crystal display device with high contrast, brighter and brighter can be realized.

  Then, the inventor uses the color filter structure including a high-contrast filter having a specific chromaticity and a color filter having a chromaticity matched to the chromaticity of the high-contrast filter, thereby greatly improving the contrast. And the present invention has been found out that both improvement of the color reproduction range can be achieved.

  That is, the gist of the present invention is a color filter structure used in a liquid crystal display device, and a color filter formed as an aggregate of fine regions corresponding to red, green, and blue pixels colored using a pigment; The color of the red, green and blue fine regions of the color filter, which is composed of a high-contrast filter in which a dye having an absorption peak in the visible wavelength region is monomolecularly dispersed in a resin and is measured using a CIE standard C light source The white display chromaticity based on the degree is x ≦ 0.35 and y ≦ 0.38 in x and y in the CIE XYZ color system, and the chromaticity of the high contrast filter measured using the C light source is In x and y, 0.30 ≦ x, y ≦ 0.45, and the chromaticity as a color filter structure measured using the C light source is in x and y. It resides in the color filter structure, characterized in that a .25 ≦ x ≦ 0.35,0.28 ≦ y ≦ 0.38.

Another gist of the present invention includes a surface light source device using a three-wavelength light source, a liquid crystal panel, and a high-contrast film and a color filter disposed in the optical path of light emitted from the light source. The liquid crystal display device has a chromaticity of 0.25 ≦ x and y ≦ 0.35 in x and y in the CIE XYZ color system when measured in white when measured at a viewing angle of 2 degrees.
In the liquid crystal display device, the chromaticity when the light source is turned on with the color filter removed is 0.30 <x, y ≦ 0.45.

  Another gist of the present invention resides in a liquid crystal display device having a surface light source device, a liquid crystal panel, and the color filter structure of the present invention.

  Thus, according to the present invention, by using a color filter structure including a high-contrast filter having a specific chromaticity and a color filter having a chromaticity matched to the chromaticity of the high-contrast filter, a high color can be obtained. Reproducibility and contrast can be realized at the same time.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
First, an outline of the present invention will be described.
As described above, the color filter according to the present invention includes a first functional layer corresponding to a conventional color filter configured using a pigment, and a dye (monomolecularly dispersed in a resin other than the pigment ( And a second functional layer constituted by using a dye), and realizes color reproducibility required as a color filter by a combination with the first and second functional layers. Therefore, when one of the functional layers does not exist, proper color display is not achieved even when applied to a liquid crystal display device.

  In the present invention, the liquid crystal display device from which the color filter has been removed or the liquid crystal display device from which the color filter has been removed refers to a monochrome liquid crystal display device capable of displaying white with appropriate chromaticity. It means a configuration equivalent to the state in which a contrast film is applied.

Alternatively, only the color filter in the color liquid crystal display device, or a panel having a color filter (usually a liquid crystal panel), except for a state (cooling state) that can affect the display color of other displays. A state in which a surface light source device including a cathode tube, a light guide plate, a diffusion plate, and the like, various optical films including a high contrast film according to the present invention (described later), and a film bonded to the front and back surfaces of a liquid crystal panel are combined. .
The state in which the liquid crystal display device excluding the color filter is turned on means a state in which the light source is turned on and the light from the light source is emitted without being blocked.

  The white display state means a state in which white is displayed in the above-described configuration in which the color filter is provided in the liquid crystal display device excluding the color filter, that is, the configuration as the color liquid crystal display device including the color filter. To do. In other words, it is the same calculation result obtained from the transmitted light of each color or the state in which white is displayed using the red, green and blue light obtained by transmitting through the color filter. Both are in the state of maximum brightness.

  In the following description, in order to prevent confusion, a structure in which the first functional layer is a color filter, the second functional layer is a high contrast filter, and the first and second functional layers are combined is a color filter structure. I will call it the body.

  The color filter as the first functional layer in the present invention is an aggregate of fine regions of blue, green and red, and a state in which white display is performed on a liquid crystal display device to which the color filter is applied, that is, the color filter is A state in which white is displayed using red, green, and blue light obtained by transmission or an equivalent calculation result obtained from transmitted light of each color has a specific chromaticity.

  Specifically, the chromaticity of the composite color (white) in a state where the red, green, and blue light transmitted through the color filter has the maximum luminance is represented by x, y (x = X / X) in the CIE XYZ color system. (X + Y + Z), y = Y / (X + Y + Z)) are both 0.35 or less (x, y ≦ 0.35), preferably 0.33 or less (x, y ≦ 0.33), more preferably 0.31 or less (x, y ≦ 0.31).

  The high-contrast filter as the second functional layer in the present invention has a chromaticity of transmitted light measured using a CIE standard C light source as a light source, and the x and y values in the CIE XYZ color system are 0.30 ≦ x, y ≦ 0.45, preferably 0.30 ≦ x, y ≦ 0.40, more preferably 0.30 ≦ x ≦ 0.35, and 0.32 ≦ y ≦ 0.37.

  The high-contrast filter has an absorption peak in the range of 380 nm to 780 nm of visible light of 455 nm to 540 nm, a half width of 50 nm or less, and a transmittance at the absorption peak of 70% or less, preferably 50% or less, more preferably 30 % Or less is preferable. The absorption characteristics of the high contrast filter according to the present invention are not due to the pigment but to the pigment (dye) dispersed in a monomolecular manner in the resin. This absorption also absorbs the blue-green sub-emission peak (490 nm) existing between the blue emission peak (450 nm) and the green emission peak (545 nm) of the three-wavelength fluorescent tube.

  Further, the chromaticity measured as the color filter structure of the present invention combining the color filter and the high contrast filter is 0.25 in a state where white display is performed on the color liquid crystal display device to which the color filter structure is applied. ≦ x, y ≦ 0.35. This means that proper color display in the CIE XYZ color system can be achieved by combining the color filter and the high contrast filter.

  The absorption spectrum of the above-described high contrast filter is an absorption spectrum that has been realized by adding a pigment to a conventional color filter. As a result, the amount of pigment used in the color filter can be reduced.

  Light scattering by the pigment increases as the wavelength of the light is shorter. Accordingly, among the emission peaks of the three-wavelength emission type fluorescent tube, blue emission is most easily scattered. Therefore, among the pigments for realizing the blue, green, and red pixel regions constituting the color filter, the blue pixel region pigment (that is, the pigment for absorbing components other than the blue emission peak) is reduced. This is most effective for increasing the transmittance of the color filter and thus the contrast of the color liquid crystal display device. For this reason, in the present embodiment, it is possible to reduce the total amount of violet pigment, which is a main factor that makes it difficult to atomize and deteriorates contrast by using a high contrast filter. As a result, as described later, a high-contrast color liquid crystal display device is realized.

  Of course, the absorption spectrum of not only the blue pixel area but also the pigment added to the green and red pixel areas (especially the pigment added to remove the sub-emission peak) is realized by the high contrast filter. It is also possible to reduce part or all of the pigment to be applied. Specifically, if a high-contrast filter having an absorption peak of 560 nm to 620 nm and a half width of 50 nm or less is used, a green emission peak (545 nm) and a red emission peak (610 nm) of a three-wavelength fluorescent tube are used. It can absorb the orange sub-emission peak (585nm) located between them, and the color filter adjusted for this (that is, using the pigment that has been used in the past to realize the absorption characteristics realized by the high contrast filter) It is also possible to manufacture a color filter) and a liquid crystal display using the same.

  A high-contrast filter for removing multiple sub-emission peaks can be realized by any method, but the simplest method is to stack a plurality of high-contrast filters that remove individual sub-emission peaks. It is.

Hereinafter, details of the present invention will be described together with a configuration of a transmissive color liquid crystal display device as a specific application example of the color filter structure according to the present invention.
FIG. 1 is a schematic view showing an example of a sectional structure of a transmissive color liquid crystal display device according to this embodiment.

  The transmissive liquid crystal display device includes a liquid crystal cell unit (liquid crystal display panel) 10 and a surface light source device (backlight) 11 that provides a surface light source to the liquid crystal cell unit 10. The liquid crystal cell unit 10 is formed in a layered structure like sandwiches, and includes a polarizing plate 19, a glass substrate 20, a color filter 21, a liquid crystal layer 22, a glass substrate 23, and a polarizing plate 24 in order from the surface side. .

  As shown in FIGS. 1 and 8, a typical surface light source device 11 includes a light source 2 that is a linear light source 2 along a side end surface of a substrate made of a light-transmitting flat plate, that is, one side end of the light guide 1. The reflector 3 is attached so as to cover the linear light source 2, and the direct light from the linear light source 2 and the reflected light reflected by the reflector 3 are transmitted to the light guide 1 at the light incident end face 1 a. The light enters the inside from a certain one end face. One surface of the light guide 1 is a light emitting surface 1b, and a light collecting film 5 having a substantially triangular prism-shaped array (light collecting element) 4 formed on the surface of the light emitting surface 1b. It is installed with the apex angle facing the viewer. On the other hand, on the surface 1c on the opposite side of the light emitting surface 1b of the light guide 1, light having a plurality of dots 6a, 6a, 6a,... Printed in a predetermined pattern with light scattering ink as shown in FIG. A take-out mechanism 6 is provided. Further, a light reflecting sheet 7 is disposed on the surface 1c side opposite to the light emitting surface 1b of the light guide 1 where the light extraction mechanism 6 is formed in the vicinity of the surface 1c. In the example of FIG. 1, the high contrast filter 18 is provided on the lower surface of the light diffusion sheet 9 of the surface light source device 11.

When the above-described high contrast filter is applied to the liquid crystal display device having such a configuration, one of the following forms is conceivable.
(1) A high contrast filter formed by dissolving a pigment in a binder resin is disposed in the optical path.
(2) A coating solution in which a dye is dissolved in a binder resin is used for an optical system element generally used in a transmissive liquid crystal display device, for example, a light guide for a surface light source device, a reflective sheet, a light diffusion sheet, a condensing sheet, a polarizing film, A high contrast filter (high contrast layer) is formed by coating the upper or lower surface of an antireflection film, a viewing angle widening film, a retardation film or the like.
(3) By mixing pigments in the production of optical system components generally used in transmissive liquid crystal display devices, light guides of surface light source devices, light diffusion sheets, polarizing films, antireflection films, viewing angle widening films, etc. These components themselves have the function of a high contrast filter.

  As the binder resin in (1) or (2), any dye can be used as long as it has high transparency and a dye having a desired absorption spectrum can stably exist in a molecular form in the resin, that is, has high compatibility with the dye. Can be used. Examples thereof include acrylic resins, polycarbonate resins, polyester resins, polyvinyl alcohol resins, polyolefin resins, polyimide resins, melamine resins, silicate resins, and the like.

  As a method for forming a layer containing a dye, the above resin and the dye are dissolved in a common solvent, and then applied and dried. The monomer and the dye that are the precursors of the resin are applied and cured by heat or light. Methods and the like.

  In the case of (3), the film itself is colored to a desired color by kneading with a pigment before forming a polarizing film, a light diffusion sheet, a viewing angle widening film, an antireflection film, a retardation film, etc. into a film shape. Can be obtained by the method. In the case of a light guide plate, it can be obtained by kneading with a pigment before processing into a plate shape by injection molding or the like. In the case of a light diffusing sheet, since a coating layer made of a photocurable resin in which almost transparent beads are dispersed is formed on a base film (such as a PET film), a pigment is mixed in advance with this coating solution, The coating layer may be colored, or the substrate film itself may be colored.

  A particularly preferable aspect with high productivity is an aspect in which the light diffusion sheet and / or the light collecting sheet used in the surface light source device have a function of a high contrast filter. Specifically, in the coating of the binder resin solution and the coating of the photocurable resin that are performed in the process of producing these sheets, a pigment is added to the coating liquid without adding a new process (2 The high-contrast filter (high-contrast layer) of the present invention can be easily obtained in the form of

  The constituent elements of these embodiments will be described in more detail. First, the light diffusing sheet and the light collecting sheet are pigments having an absorption band at a specific wavelength in the visible light region on a thermoplastic resin base film excellent in moldability. At least one pigment dispersion layer in which is dispersed is provided.

  Here, as a base film made of a thermoplastic resin, it has high transparency while maintaining an appropriate rigidity, and when receiving heat generated from a light source, that is, a discharge tube such as a cold cathode tube. A material that does not bend is preferable. Specifically, a film made of polyethylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyarylate, norbornene-based cyclic polyolefin, polymethyl methacrylate, etc. having a thickness of 30 μm to 350 μm, preferably 40 μm to 300 μm, more preferably 50 μm to 250 μm. Among them, a biaxially stretched polyethylene terephthalate film or a biaxially stretched polypropylene film is most suitable because it has high rigidity and is firm, and is less susceptible to heat deflection.

  In addition, as shown in FIG. 1, the light diffusing sheet or the light collecting sheet in the present invention is installed on the light emitting surface 1b of the surface light source device, and the light diffusing sheet expands the emission angle distribution of the surface light source device. The light collecting sheet has an effect of improving the luminance in the normal direction of the surface light source device. That is, in a transmissive or transflective liquid crystal display device having RGB color filters, an optical member that causes illumination light loss such as a color filter or a polarizing film when illumination light emitted from a back surface light source device (backlight) is provided. In order to transmit, the backlight must be as efficient as possible, guiding the illumination light in the normal direction of the light exit surface, and having a characteristic of maintaining a proper exit angle distribution that does not give a sense of incongruity as a display device. Because it will not be.

  Here, as a more specific configuration of the light diffusion sheet, as shown in FIG. 2, a mode in which transparent beads made of acrylic resin, silicone resin, etc. are coated so as to have an appropriate haze is preferable. The high contrast filter of the present invention can be obtained by dispersing and coating a pigment in a bead-containing coating solution. At this time, the light diffusibility of the transparent beads is desirably in the range of 5% to 90%, preferably 10% to 85%, more preferably 15% to 80%, based on ASTM D1003.

  In addition, as a guide of the light condensing effect in the light condensing sheet, as shown in FIG. 3, the luminance in the normal direction of the light emitting surface 1b without installing anything on the light emitting surface 1b of the surface light source device. As shown in FIG. 3 (b), the condensing sheet 5 is placed directly on the light guide 1 as compared with the brightness measured directly on the light guide 1 when the brightness is measured by the brightness measuring device 11 ′. When installed, the luminance increase rate is preferably at least 1.1 times or more, more preferably 1.15 times or more, and still more preferably 1.2 times or more. That is, by collecting the emitted light beam from the surface light source device intensively in the front direction by the light collecting sheet 5, the brightness of the display image can be kept high even if there is a color filter or the like on the liquid crystal panel. It becomes.

  As a specific structure of this condensing sheet, as shown in FIG. 4, an embodiment in which the condensing element 4 made of a fine triangular prism array is formed on the surface of the base film 5a, as shown in FIG. An embodiment in which the condensing element 4 made of a fine corrugated array is formed on the surface portion of the base film 5a, as shown in FIG. 6B, the condensing element 4 made of a fine lenticular lens array is used as the base material FIG. 6 (c) shows an embodiment in which the surface of the film 5a is formed, as shown in FIG. 6 (a), an embodiment in which the condensing element 4 made of a micro lens array is formed on the surface of the base film 5a. As shown in the drawing, a typical example is a mode in which the condensing element 4 formed of a fine pyramid and / or a conical array is formed on the surface portion of the base film 5a, and is disposed on the light emitting surface 1b of the surface light source device. Brightness increase rate of at least 1.1 times So that, parietal angle, etc. of the prism array is suitably are designed.

  Furthermore, as shown in FIG. 2, a mode in which a substantially spherical bead 12 having a lens effect (front brightness increasing effect) is formed by coating the surface layer of the base film 5a with a binder resin is also suitable. Therefore, it is possible to obtain a light-collecting sheet that is extremely suitable for applications such as a liquid crystal television having both excellent light diffusibility and a front luminance increase effect.

More specifically, as shown in FIG. 2, in an embodiment in which the substantially spherical beads 12 having a lens effect (brightness increasing effect) are formed by coating the surface layer of the base film 5a with a binder resin, the beads The particle size of 12 is usually in the range of 0.1 μm to 100 μm, preferably 0.5 μm to 70 μm, more preferably 1.0 μm to 50 μm, and as shown in FIG. It is preferable that the coating is arranged in a plane without being coated.
Furthermore, as shown in FIG. 4, in the embodiment in which the condensing element 4 composed of a fine triangular prism array is formed on the surface portion of the base film 5 a, the arrangement pitch of the prism array is preferably 5 μm to 150 μm, more preferably A range of 15 μm to 100, more preferably 25 μm to 75 μm is preferably used, and the apex angle of the prism portion is preferably 65 ° to 150 °, more preferably 70 °, when the apex of the prism is arranged upward. The range of degrees to 140 degrees, more preferably 75 degrees to 130 degrees is preferably used. In the case where the apex of the prism is arranged downward, it is preferably 50 degrees to 80 degrees, more preferably 55 degrees to A range of 75 degrees, more preferably 60 degrees to 70 degrees is preferably used.

  In the production of the above-described light diffusing sheet and light collecting sheet, which are preferred embodiments of the present invention, it is preferable to use a binder resin coating step and a photocurable resin coating + curing step. As described above, a high contrast filter can be obtained by introducing a dye into the coating liquid based on an appropriate relationship with the color filter spectrum.

  Specific examples of suitable binder resins include polyacrylate resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins, AS resins, polyester resins, and the like. Can be mentioned.

  In addition, more specific examples of suitable photopolymerizable monomers include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like. As photopolymerization initiators, acetophenone series, Typical examples include benzoin and benzophenone. Furthermore, it goes without saying that when these binder resins and photopolymerizable monomers are selected, those having good dispersibility with respect to the dye should be selected.

  In addition, it is particularly desirable that the light diffusion sheet and the light collecting sheet according to the present invention are disposed with an air layer provided on the light emission surface of the surface light source device. This is particularly important in a sidelight type surface light source device. As shown in FIG. 8, when the light diffusion sheet and the light collecting sheet 5 are arranged on the light guide 1, a very slight air layer a is formed. By making it exist, the phenomenon that the illumination light beam (indicated by the arrow) propagating in the light guide 1 by the air layer a enters the light collecting sheet 5 as shown in FIG. Is suppressed. This prevents the phenomenon that the illumination light propagating in the light guide 1 for a long distance repeats the interaction with the high contrast filter many times, and the wavelength characteristic of the illumination light beam is changed between the area close to the light source and the area far from the light source. Therefore, even when applied to a large liquid crystal display, it is possible to achieve high uniformity of optical characteristics (color reproducibility) within the image plane.

  Here, as a method of disposing the light diffusion sheet and the condensing sheet by providing an air layer a on the light emitting surface 1b of the surface light source device, an uneven process is performed on the side of the condensing sheet 5 in contact with the light emitting surface 1b. The method of applying is preferable. For example, as shown in FIGS. 2, 4, and 5, a typical embodiment is a method in which a coating liquid composed of light and / or thermosetting resin in which substantially transparent beads 13 are dispersed is applied and cured to perform uneven processing. However, in addition to this, the surface in contact with the light guide 1 is subjected to a matting process to be uneven, a binder resin and substantially transparent beads are dispersed in a solvent, and the solvent is evaporated after coating. A typical method is to leave the binder resin. 2, 4, and 5, reference numeral 14 indicates a coating liquid and a binder resin.

  As the thickness of the air layer a formed between the light emitting surface 1b of the surface light source device and the sheet 5, the gap measured as shown in FIG. 10 is 1 μm to 70 μm, more preferably 2 μm to 50 μm, still more preferably 3 μm. The illumination light flux propagating into the light guide 1 is devised so as not to enter the pigment dispersion layer 5b.

As the dye used in the high-contrast filter of the present invention, a dye compound having excellent absorption wavelength controllability in the visible light region and having a narrow half-width of the absorption spectrum and a sharp absorption peak is suitable. An appropriate optical design is made in relation to a pigment-dispersed color filter, which will be described later, and a liquid crystal display element excellent in high color reproducibility and brightness balance can be obtained. Speaking of pigments used in high contrast filters, squarylium compounds (diphenyl squarylium compounds, pyrazole squarylium compounds), porphyrins, azaporphyrins, diazaporphyrins, tetraazaporphyrins, dipyrromethene metal chelates, pyromethene compounds Etc.
For example, as a diphenyl squarylium compound suitable for use at the boundary between red and green, a compound of the following general formula (I) shown as [Chemical Formula 1] can be given as a representative example.

[In Formula (I), R ¹ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An allyoloxy group which may have, or a halogen atom is shown. Here, adjacent R ¹ may be taken together to form an alkanediyl group or an alkylenedioxy group. R ² represents a hydrogen atom or a monovalent substituent, and G ¹ represents a group represented by —NR ³ — (wherein R ³ represents a hydrogen atom or an alkyl group), or oxygen An atom, and G ² represents a carbonyl group or a sulfonyl group (here, when G ² is a sulfonyl group, R ² is not a hydrogen atom). m, n, and p are integers of 0 or more, and m + n + p is 5 or less. However, these substituents on the benzene ring may be different from each other with respect to the other benzene ring, and when m and n are 2 or more in one benzene ring, R ¹ and G ¹ -G group represented by ² -R ² may be different from each other between the other substituents in the same ring. ]

  More specifically, compounds of the general formulas (I-1) to (I-56) represented by [Chemical Formula 2] to [Chemical Formula 9] are given as typical examples.

  A typical example of the tetraazaporphyrin-based compound suitable for removing the sub-luminescence generated in the boundary region between red and green is a compound of the general formula (II) represented by [Chemical Formula 10].

[In the formula (II), R ^{1 to} R ⁸ each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an alkyl group which may have a substituent, or a substituent. An alkoxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent A dialkylamino group optionally having a substituent, an alkylthio group optionally having a substituent, or an arylthio group optionally having a substituent, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ may be linked to form an aliphatic carbocycle. M represents two hydrogen atoms, a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom. ]

  More specifically, compounds represented by the general formulas (II-1) to (II-9) represented by [Chemical Formula 11] are given as representative examples.

  A typical example of a pyrazole-based squarylium compound suitable for removing the sub-luminescence generated in the boundary region between blue and green is a compound of the general formula (III) represented by [Chemical Formula 12].

[In Formula (III), Y ₁ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and each Y ₁ may be the same. May be different. Y ₂ has a hydrogen atom, an alkyl group which may have a substituent, an amino group which may have a substituent, an alkoxycarbonyl group which may have a substituent, or a substituent. Each Y ₂ may be the same or different. X represents an -O- or -NH- group. ]

  More specifically, compounds represented by the general formulas (III-1) to (III-8) represented by [Chemical Formula 13] are given as typical examples.

  Here, these squarylium compounds are disclosed in, for example, Angew. Chem. 77 680-681 (1965), or according thereto. These tetraazaporphyrin-based dyes are disclosed in J. Org. Gen. Chem. USSR vol. 47, 1954-1958 (1977).

  Further, the porphyrin compound having a maximum absorption wavelength at 440 to 510 nm, which is suitable for removing the sub-light emission generated in the boundary region between blue and green, is not particularly limited, but the green emission wavelength of 530 to 550 nm and blue It is desirable not to have an absorption maximum at the emission wavelength of 420 to 440 nm. Particularly preferred compounds include porphyrin compounds represented by the following general formula (IV).

[Wherein, X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, an alkoxy group, an alkylthio group, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted naphthoxy group, a substituted or unsubstituted phenylthio group, or Represents a substituted or unsubstituted naphthylthio group, R represents a substituted or unsubstituted phenyl group, M represents two hydrogen atoms, or a divalent metal, trivalent, or tetravalent metal derivative; ]

Specific examples of the porphyrin compound represented by the general formula (1) used in the present invention are described below. Examples of the halogen atom in X _{1 to} X ₈ include fluorine, chlorine, bromine and iodine. The alkoxy group and thioalkyl group are not particularly limited, but the alkyl group in the substituent is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and having 1 to 8 carbon atoms. A linear, branched or cyclic alkyl group is particularly preferred.

  Specific examples of the alkyl group in the alkoxy group and thioalkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group. Group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2 , 2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethyl Tyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-methyl Hexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-octyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-di- Tyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl Group, 2,2,5,5-tetramethylhexyl group, 1-cyclopentyl-2,2-dimethylpropyl group, 1-cyclohexyl-2,2-dimethylpropyl group and the like.

  Specific examples of the substituted or unsubstituted phenoxy group include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethyl. Examples include phenoxy group, 2,4-dimethylphenoxy group, 3,4-dimethylphenoxy group, 4-t-butylphenoxy group, 4-aminophenoxy group, 4-dimethylaminophenoxy group, 4-diethylaminophenoxy group and the like.

  Specific examples of the substituted or unsubstituted naphthoxy group include 1-naphthoxy group, 2-naphthoxy group, nitronaphthoxy group, cyanonaphthoxy group, hydroxynaphthoxy group, methylnaphthoxy group, trifluoromethylnaphthoxy group and the like. .

  Specific examples of the substituted or unsubstituted phenylthio group include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-ethylphenylthio group, and a 3-ethylphenylthio group. Group, 4-ethylphenylthio group, 2,4-dimethylphenylthio group, 3,4-dimethylphenylthio group, 4-t-butylphenylthio group, 4-aminophenylthio group, 4-dimethylaminophenylthio group , 4-diethylaminophenylthio group and the like.

  Specific examples of the substituted or unsubstituted naphthylthio group include 1-naphthylthio group, 2-naphthylthio group, nitronaphthylthio group, cyanonaphthylthio group, hydroxynaphthylthio group, methylnaphthylthio group, trifluoromethylnaphthylthio group. Etc.

  R is a substituted or unsubstituted phenyl group, and specific examples thereof include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethyl. Phenyl group, 4-ethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-t-butylphenyl group, 4-aminophenyl group, 4-dimethylaminophenyl group, 4-diethylaminophenyl Groups and the like.

M represents two hydrogen atoms, or a divalent metal, trivalent, or tetravalent metal derivative, and as M is a divalent metal, Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II), trivalent or tetravalent metal derivatives include AlCl, InCl, FeCl , MnCl, SiCl ₂ , GeCl ₂ , TiO, Vo and the like.
Although the representative example of general formula (IV) is shown in the following table | surface (Table 1-Table 8), it is not limited to these.

  Further, the azaporphyrin-based and diazaporphyrin-based compounds having a maximum absorption wavelength at 570 to 605 nm suitable for removing the sub-light emission generated in the boundary region between red and green are not particularly limited. It is desirable that there is no absorption maximum at a certain 610-630 nm. Particularly preferred compounds include azaporphyrin compounds represented by the following general formula (V) (Chemical Formula 15).

[Wherein, X _{1 to} X ₈ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, an alkyl group having 20 or less carbon atoms, an alkoxy group, an aryl group. It represents an oxy group, monoalkylamino group, dialkylamino group, aralkyl group, aryl group, heteroaryl group, alkylthio group, arylthio group, acyl group or alkoxycarbonyl group. R _{1 to} R ₄ each independently represent a carbon atom or a nitrogen atom. However, one or two nitrogen atoms are included among R _{1 to} R ₄ . M represents two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal. ]

Azaporphyrin compound represented by the general formula (V) used in the present invention, in the substituent represented by R ₁ to R _4, mono- azaporphyrin one is a nitrogen atom of R ₁ to R ₄ or If it is a diazaporphyrin in which two are nitrogen atoms, the other substituents are not particularly limited, but are specifically described below.
Hydrogen atom; halogen atom of fluorine, chlorine, bromine, iodine; nitro group; cyano group; hydroxyl group; amino group; carboxyl group; sulfonic acid group methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl Group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group Group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclo- Hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-nonyl group, 3,5,5-trimethylhexyl group N-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetramethyl Ruoctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2 A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as 1,2-dimethylpropyl group; methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-do Decyloxy group, methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group, 3-methoxypropyl group, 2-methoxybutyl group, methoxyethoxy group, ethoxyethoxy group, 3-methoxypropyloxy group, 3- (iso- C 1-20 alkoxy group such as propyloxy) propyloxy group; phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso- Aryloxy groups having 6 to 20 carbon atoms such as propylphenoxy group; monoalkyls having 1 to 20 carbon atoms such as methylamino group, ethylamino group, n-propylamino group, n-butylamino group and n-hexylamino group Amino group; dimethylamino group, diethylamino group, di-n-propylamino group, di C2-C20 dialkylamino groups such as n-butylamino group, N-methyl-N-cyclohexylamino group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, Trimethylbenzyl, dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluoromethylbenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, hydroxynaphthylmethyl, methylnaphthylmethyl, trifluoromethylnaphthyl Aralkyl group having 7 to 20 carbon atoms such as methyl group; phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, dichlorophenyl group, methoxyphenyl group Carbon number such as nyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group 6-20 aryl groups; pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazolyl group, benzofuranyl group, indoyl group and other heteroaryl groups; methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo -Pentylthio group C 1-20 alkylthio group such as 1,2-dimethylpropylthio group; 6 carbon atoms such as phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group, 4-t-butylphenylthio group ~ 20 arylthio groups; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl Group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group and other acyl groups having 1 to 20 carbon atoms; methoxycarbonyl group, ethoxycarbonyl group, Isopropyloxycarbonyl group, 2,4-dimethyl It may be mentioned an alkoxycarbonyl group having from 2 to 20 carbon atoms such as butyl oxycarbonyl group and the like.

Examples of the divalent metal represented by M include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II), etc. are mentioned.
Examples of monosubstituted trivalent metals include Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-Br, Ga-F, Ga-I, In-Cl, In-Br. , In-F, In-I , Tl-Cl, Tl-Br, Tl-F, Tl-I, Al-Cl, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In-C _{6 H 5, In-C 6} H 4 (CH 3), Mn (OH), Mn (OC 6 H 5), Mn (OSi (CH 3) 3), Fe-Cl, include Ru-Cl, etc..

Examples of 2 substituted 4 metals include CrCl ₂ , SiCl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , GeF ₂ , GeI ₂ , SnCl ₂ , SnF ₂ , SnBr ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof. ], Si (OR ′) ₂ , Sn (OR ′) ₂ , Ge (OR ′) ₂ , Ti (OR ′) ₂ , Cr (OR ′) ₂ [R ′ is an alkyl group, phenyl group, naphthyl group, A trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof are represented. ], Sn (SR ") ₂ , Ge (SR") ₂ , [R "represents an alkyl group, a phenyl group, a naphthyl group, and its derivative.] Etc. are mentioned.
Examples of the oxymetal include VO, MnO, TiO and the like.

  Representative examples of the general formula (V) are shown in the following tables (Tables 9 to 12).

  In addition, the dipyrromethene metal chelate compound having a maximum absorption wavelength at 440 to 510 nm suitable for reducing the amount of dioxazine violet used is not particularly limited, but at a green emission wavelength of 530 to 550 nm and a blue emission wavelength. It is desirable that there is no absorption maximum at a certain 420 to 440 nm. A particularly preferred compound is a dipyrromethene metal chelate compound represented by the following general formula (VI) (Chemical Formula 16).

[Wherein R _{1 to} R ₇ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, an alkyl group having 20 or less carbon atoms, an alkoxyalkyl group, Alkoxy group, alkoxyalkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, alkylaminocarbonyl group, dialkylaminocarbonyl group, alkylcarbonylamino group, phenylcarbonylamino group, phenylaminocarbonyl group, phenoxycarbonyl group, aralkyl group, Represents an aryl group, a heteroaryl group, an alkylthio group, a phenylthio group or an alkenyl group, and M represents a divalent metal atom. ]

Specific examples of the dipyrromethene metal chelate compound represented by the general formula (VI) used in the present embodiment are described below.
R _{1 to} R ₇ include a hydrogen atom; a halogen atom of fluorine, chlorine, bromine, or iodine; a nitro group; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a sulfonic acid group, a methyl group, an ethyl group, an n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2- Methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-octyl group, 3,5 , 5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n-undecyl group, n Dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n -Pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2 -Linear, branched or cyclic alkyl groups such as dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group; methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group, 3-methoxypropyl group , Alkoxyalkyl groups such as 2-methoxybutyl group; methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n -Alkoxy groups such as butoxy, iso-butoxy, sec-butoxy, t-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy, n-hexyloxy, n-dodecyloxy; Alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, 3-methoxypropyloxy group, 3- (iso-propyloxy) propyloxy group; phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t Aryloxy groups such as butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group; formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl Group, iso-butylcarbonyl group, sec- Acyl groups such as tilcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group; methoxycarbonyl group, ethoxycarbonyl Group, alkoxycarbonyl group such as isopropyloxycarbonyl group and 2,4-dimethylbutyloxycarbonyl group; methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, n-hexylamino Alkylaminocarbonyl group such as carbonyl group; dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, N-methyl-N-cyclohe Dialkylaminocarbonyl group such as xylaminocarbonyl group; alkylcarbonylamino group such as acetylamino group, ethylcarbonylamino group, butylcarbonylamino group; phenylaminocarbonyl group, 4-methylphenylaminocarbonyl group, 2-methoxyphenylaminocarbonyl Group, phenylaminocarbonyl group such as 4-n-propylphenylaminocarbonyl group; phenylcarbonylamino group such as phenylcarbonylamino group, 4-ethylphenylcarbonylamino group, 3-butylphenylcarbonylamino group; phenoxycarbonyl group, 4 -Phenoxycarbonyl group such as t-butylphenoxycarbonyl group; benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group Trimethylbenzyl, dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluoromethylbenzyl, naphthylmethyl, nitronaphthylmethyl, cyanonaphthylmethyl, hydroxynaphthylmethyl, methylnaphthylmethyl, trifluoromethylnaphthyl Aralkyl groups such as methyl groups; phenyl groups, nitrophenyl groups, cyanophenyl groups, hydroxyphenyl groups, methylphenyl groups, dimethylphenyl groups, trimethylphenyl groups, dichlorophenyl groups, methoxyphenyl groups, ethoxyphenyl groups, trifluoromethylphenyl groups Aryl such as N, N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group, etc. A heteroaryl group such as a pyrrolyl group, a thienyl group, a furanyl group, an oxazoyl group, an isoxazoyl group, an oxadiazoyl group, an imidazolazoyl group, a benzoxazoyl group, a benzothiazoyl group, a benzoimidazolyl group, a benzofuranyl group, an indoyl group; a methylthio group , Ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group Alkylthio groups such as 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group; phenylthio group, 4-methylphenylthio group, 2-methoxyphenylthio group 4-t-butylpheny group Phenylthio group such as ruthio group; vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxyl vinyl group, 2-cyano-2-methylsulfonvinyl group and the like.

  Examples of the divalent metal represented by M include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Sn (II), etc. are mentioned.

  Representative examples of general formula (VI) are shown in the following tables (Tables 13 to 14).

Examples of the pyromethene compound include a compound represented by the following formula (VII).

[Wherein, R ^{1 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. -20 halogenoalkyl group, C1-C20 alkoxy group, C2-C20 alkenyl group, C2-C20 alkoxyalkyl group, C2-C20 alkoxyalkoxy group, C6-C20 Aryloxy group, C1-C20 acyl group, C2-C20 alkoxycarbonyl group, C2-C20 alkylaminocarbonyl group, C3-C20 dialkylaminocarbonyl group, C2-C2 20 alkylcarbonylamino groups, 7-20 carbon atoms phenylcarbonylamino group, 7-20 carbon atoms phenylaminocarbonyl group, 7-20 carbon atoms A phenoxycarbonyl group, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a phenylthio group having 6 to 20 carbon atoms, C3-C20 alkenyloxycarbonyl group, C8-C20 aralkyloxycarbonyl group, C4-C20 alkoxycarbonylalkoxycarbonyl group, C4-C20 alkylcarbonylalkoxycarbonyl group, C2-C2 20 mono (hydroxyalkyl) aminocarbonyl groups, 3 to 20 carbon di (hydroxyalkyl) aminocarbonyl groups, 3 to 20 carbon mono (alkoxyalkyl) aminocarbonyl groups, or 5 to 20 carbon di (alkoxy) Alkyl) aminocarbonyl group, R ² and R ³ and / or R ⁵ R ⁶ may be bonded to each other to form an aromatic ring condensed with a pyrrole ring, and the condensed aromatic rings formed by these may be the same or different, Formula (a)

(Wherein R ^{8 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom) -20 halogenoalkyl group, C1-C20 alkoxy group, C2-C20 alkenyl group, C2-C20 alkoxyalkyl group, C2-C20 alkoxyalkoxy group, C6-C20 Aryloxy group, C1-C20 acyl group, C2-C20 alkoxycarbonyl group, C2-C20 alkylaminocarbonyl group, C3-C20 dialkylaminocarbonyl group, C2-C2 20 alkylcarbonylamino groups, 7-20 carbon atoms phenylcarbonylamino group, 7-20 carbon atoms phenylaminocarbonyl group, 7-20 carbon atoms A phenoxycarbonyl group, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a phenylthio group having 6 to 20 carbon atoms, C3-C20 alkenyloxycarbonyl group, C8-C20 aralkyloxycarbonyl group, C4-C20 alkoxycarbonylalkoxycarbonyl group, C4-C20 alkylcarbonylalkoxycarbonyl group, C2-C2 20 mono (hydroxyalkyl) aminocarbonyl groups, 3 to 20 carbon di (hydroxyalkyl) aminocarbonyl groups, 3 to 20 carbon mono (alkoxyalkyl) aminocarbonyl groups, or 5 to 20 carbon di (alkoxy) alkyl) aminocarbonyl group, R ¹⁰ and R ¹¹ are each each other Bind to represent an aromatic ring may be formed). ]

  Furthermore, in the present invention, in order to further improve color reproducibility and obtain a vivid display image, it is more preferable to dispose a dye that selectively absorbs even in the vicinity of a wavelength of 400 nm in the organic dye dispersion layer.

  As this dye, for example, a dipyrazolylmethine dye of the general formula (VIII) represented by [Chemical Formula 19] is suitable.

[In Formula (VIII), R ⁹ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, and R ¹⁰ has a substituent. An optionally substituted alkaryl group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryl group, an aryloxy group, and a substituent. An aryloxycarbonyl group which may have, an amino group which may have a substituent, or a hydrogen atom, R ¹¹ has an alkyl group which may have a substituent, or a substituent. An optionally substituted cycloalkyl group, an optionally substituted aryl group or a hydrogen atom, X represents an oxygen atom or an NH group, and these R ¹⁰ , R ¹¹ , and X represent both pyrazoles It can be different between the rings Yes. ]

More specifically, compounds represented by the general formulas (VIII-1) to (VIII-9) represented by [Chemical Formula 20] are given as typical examples.

  Here, these dipyrazolyl methine compounds are exemplified by Liebigs Ann. Chem. , 1680-1688 (1976), or in accordance therewith.

  Moreover, although the said pigment | dye is excellent in controllability of an absorption spectrum, there exists a problem which is easy to receive deterioration by light or a heat | fever. Therefore, in the present invention, it is preferable to add a so-called light stabilizer having functions such as an ultraviolet absorption function, a free radical stabilization function, and an antioxidant function to the dye dispersion layer. Here, typical light stabilizers include organic ultraviolet absorbers (benzophenone, benzotriazole, ogizanide, formamidine), inorganic ultraviolet absorbers, hindered amine light stabilizers, aryl ester light stabilizers. Agents, phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. These are preferably blended in appropriate amounts to such an extent that the optical properties are not sacrificed to suppress deterioration of the organic dye.

  More specifically, for example, organic ultraviolet absorbers include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-). t-butylphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, phenyl salsylate, 4-t-butylphenyl salsylate, 2,5-di- Examples thereof include t-butylphenyl 4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate and the like.

  Furthermore, examples of the inorganic ultraviolet absorber include titanium oxide, zinc oxide, cerium oxide, iron oxide, and barium sulfate. Here, as the ultraviolet absorber, the wavelength at which the transmittance is 50% is preferably 350 to 420 nm, more preferably 360 to 400 nm, and the ultraviolet absorbing ability is weak at wavelengths shorter than 350 nm and longer than 420 nm. The wavelength is not preferable because coloring becomes strong.

  In addition to the mode in which the light stabilizer is blended in the pigment dispersion layer as described above, a mode is also provided in which a layer that absorbs ultraviolet rays having a significant effect on the photodegradation is provided, thereby suppressing degradation of the pigment. Is possible. That is, an embodiment in which the pigment dispersion layer 5b is sandwiched between ultraviolet absorption and / or reflection layers, an embodiment in which a pigment is dispersed in one coating layer, and an ultraviolet absorber is dispersed in the other coating layer can be implemented.

  In the present invention, in order to keep the color reproducibility and vividness of an image sufficiently high, it is preferable that the number of light absorption peaks in the visible light region by the high contrast filter is as small as possible. That is, when a filter is configured using an inorganic substance or the like, in addition to the main absorption peak, a slight absorption peak appears in an unintended portion, which causes a deterioration in color tone and the like, and a desirable wavelength cut characteristic is obtained. However, in the present invention, since the above-designed dye is used for wavelength cut, the absorption wavelength can be controlled with high accuracy, and only a specific wavelength is used. It can be absorbed selectively.

  That is, the high-contrast filter preferably has 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2 light absorption peaks in the visible light region, and cuts off an extra wavelength region. Therefore, it is possible to cut only the necessary wavelength. In the present invention, the visible light region means a wavelength region of 380 nm to 780 nm.

Next, the color filter will be described.
Color filters used in liquid crystal display devices or solid-state imaging devices form fine pixels such as red, green, and blue on transparent substrates such as glass by dyeing, printing, electrodeposition, and pigment dispersion. It is what. Further, in order to block light leakage between pixels and obtain a higher quality image, a light shielding pattern called a black matrix is often provided between the pixels.

  In the electrodeposition method, a transparent substrate such as glass provided with an electrode is immersed in a bath containing a pigment or dye, and a color filter is formed by electrophoresis. A color filter by the pigment dispersion method forms a coating film on a transparent substrate such as glass by applying a composition in which a color material such as a pigment is dispersed or dissolved in a photosensitive resin, and is irradiated with radiation through a photomask. Exposure is performed, and unexposed portions are removed by development processing to form a pattern. In addition to these methods, a polyimide resin composition in which a color material is dispersed or dissolved is applied and a pixel image is formed by an etching method, and a film on which a resin composition containing the color material is applied is attached to a transparent substrate. It can also be manufactured by a method of peeling and image exposure, developing to form a pixel image, a method of forming a pixel image by an ink jet printer printing method, and the like.

  In the production of color filters for liquid crystal display elements in recent years, the pigment dispersion method has become the mainstream because of its high productivity and excellent microfabrication properties, but the present invention can be applied to any of the above production methods using pigments. Applicable.

  The black matrix is formed by forming a chromium and / or chromium oxide (laminated) film on the entire surface of a transparent substrate such as glass by sputtering, and then removing only the color pixel portion by etching. Dispersing or dissolving the light shielding component The coated photosensitive composition is coated on a transparent substrate such as glass to form a coating film, exposed to radiation through a photomask, and unexposed portions are removed by development processing to form a pattern. There are methods, etc.

  Next, raw materials for producing a color filter will be described by taking the pigment dispersion method that has been mainstream in recent years as an example.

  In the pigment dispersion method, as described above, a composition in which a color material such as a pigment is dispersed in a photosensitive resin (hereinafter referred to as “color filter composition”) is used. In the color filter composition according to the present invention, (a) a binder resin and / or (b) a monomer, (c) a photopolymerization initiator, (d) a coloring material, and (e) other components as a solvent as a photosensitive component. It is dissolved or dispersed in. The binder resin and monomer may be appropriately selected in consideration of the color filter manufacturing process. Hereinafter, each component will be described in detail.

(A) Binder resin When a binder resin is used alone, an appropriate one is appropriately selected in consideration of the formability and performance of the target image and the production method desired to be employed. When the binder resin is used in combination with the monomer described later, the binder resin is added to improve the color filter composition and improve the physical properties after photocuring. Therefore, in this case, the binder resin is appropriately selected according to the purpose of improving compatibility, film-forming property, developability, adhesiveness and the like.

  Examples of commonly used binder resins include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide and the like. Examples of the polymer include polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolac resin, resol resin, polyvinyl phenol, and polyvinyl butyral.

  Among these binder resins, preferred are those containing a carboxyl group or a phenolic hydroxyl group in the side chain or main chain. If a resin having these functional groups is used, development with an alkaline solution becomes possible. Among them, a resin having a carboxyl group, such as an acrylic acid (co) polymer, a styrene / maleic anhydride resin, a novolak epoxy acrylate acid anhydride-modified resin, and the like, which are highly alkaline developable.

  Particularly preferred is a (co) polymer containing (meth) acrylic acid or a (meth) acrylic acid ester having a carboxyl group (referred to herein as an acrylic resin). This resin is excellent in developability and transparency, and since various copolymers can be obtained by selecting various monomers, it is easy to control performance and production method.

  Examples of the acrylic resin include (meth) acrylic acid and / or succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- ( (Meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acrylic) Leuoxypropyl) ester, adipic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ) Ester, maleic acid (2- (meth) acryloyloxypropyl) ester, succinic acid ( -(Meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxybutyl) ester, phthalic acid (2- (meta ) Acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, hydroxyalkyl (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid As an essential component, a compound to which an acid (anhydride) such as styrene is added, and if necessary, a styrene monomer such as styrene, α-methyl-styrene, vinyltoluene; cinnamic acid, maleic acid, fumaric acid, maleic anhydride, Unsaturated carboxylic acids such as itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( (Meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate , Esters of (meth) acrylic acid such as methoxyphenyl (meth) acrylate; (meth) acrylic acid added with lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone Compound that is: Acrylonitrile; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N Acrylamide such as dimethylaminoethyl acrylamide, vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl acids such as vinyl pivalate or the like, a resin obtained by copolymerizing various monomers.

  In addition, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth) for the purpose of increasing the strength of the coating film. A monomer having a phenyl group such as acrylic sulfoamide is 10 to 98 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and (meth) acrylic acid or succinic acid (2- (meta ) Acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, phthalic acid (2- (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) Ester, maleic acid (2- (meth) acryloyloxy 2 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol% of at least one monomer selected from the group consisting of (meth) acrylic acid esters having a carboxyl group such as (til) ester An acrylic resin copolymerized at a ratio of% is also preferably used. In the present invention, for example, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and (meth) acrylate, (meth) acryloyl group and the like have the same meaning.

  These resins preferably have an ethylenic double bond in the side chain. By using a binder resin having a double bond in the side chain, the photocurability of the composition for a color filter according to the present invention is increased, so that the resolution and adhesion can be further improved.

  As a means for introducing an ethylenic double bond into the binder resin, for example, a method described in JP-B-50-34443, JP-B-50-34444, or the like, that is, a glycidyl group or an epoxy is added to the carboxyl group of the resin. Examples thereof include a method of reacting a compound having both a cyclohexyl group and a (meth) acryloyl group, and a method of reacting an acrylic acid chloride with a hydroxyl group of the resin.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By reacting a compound such as acrylic acid chloride or (meth) allyl chloride with a resin having a carboxyl group or a hydroxyl group, a binder resin having an ethylenic double bond group in the side chain can be obtained. In particular, a resin obtained by reacting an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable as the binder resin.

  Thus, when an ethylenic double bond is introduced into a resin having a carboxylic acid group or a hydroxyl group in advance, the ethylenic double bond is added to 2 to 50 mol%, preferably 5 to 40 mol% of the carboxyl group or hydroxyl group of the resin. It is preferable to bind a compound having a bond.

The preferable range of the weight average molecular weight measured by GPC of these acrylic resins is 1,000 to 100,000. When the weight average molecular weight is 1,000 or less, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease. Moreover, the range of preferable content of a carboxyl group is 5-200 in an acid value. When the acid value is 5 or less, it becomes insoluble in an alkaline developer, and when it exceeds 200, the sensitivity may be lowered.
These binder resins are contained in the range of 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content of the composition of the present invention.

(B) Monomer The monomer contained in the color filter composition according to the present invention is not particularly limited as long as it is a polymerizable low molecular compound, but it is an addition having at least one ethylenic double bond. A polymerizable compound (hereinafter abbreviated as “ethylenic compound”) is preferred. The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system (described later) when the composition of the present invention is irradiated with actinic rays. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

  The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate Alicyclic diisocyanate bottles; aromatic diisocyanate bottles such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, Reaction product with hydroxy compound containing (meth) acryloyl group such as 3-hydroxy (1,1,1-trimethacryloyloxymethyl) propane And the like.

Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.
The compounding ratio of these ethylenic compounds is 10 to 80% by weight, preferably 20 to 70% by weight, based on the total solid content of the composition of the present invention.

(C) Photopolymerization initiation system When the composition for a color filter according to the present invention contains an ethylenic compound as the monomer (b), it directly absorbs light or is photosensitized to cause a decomposition reaction or hydrogen abstraction. A photopolymerization initiating system having a function of causing a reaction and generating a polymerization active radical is required.

  The photopolymerization initiation system used in the present invention is composed of a system in which an addition agent such as an accelerator is used in combination with the polymerization initiator. Examples of the polymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and 2- (2) described in JP-A-10-39503. Hexaarylbiimidazole derivatives such as' -chlorophenyl) -4,5-diphenylimidazole, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts And radical activators such as N-aryl-α-amino acid esters. Examples of the accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. A mercapto compound having a ring or an aliphatic polyfunctional mercapto compound is used. A plurality of types of photopolymerization initiator and additive may be combined.

  The blending ratio of the photopolymerization initiation system is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, more preferably 0.7 to 10% by weight, based on the total solid content of the composition of the present invention. If the blending ratio is extremely low, the sensitivity is lowered. On the other hand, if the blending ratio is extremely high, the solubility of the unexposed portion in the developer is lowered, and development failure tends to be induced.

In the composition according to the present invention, if necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be blended for the purpose of increasing the sensitivity.
Examples of these sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and heterocyclic rings described in JP-A-3-239703 and JP-A-5-289335. Coumarin dyes, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403 JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-21024. Can be cited JP, dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818.

Of these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3 Benzophenone compounds such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) ) Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- ( p-dimethylaminophenyl) benzothiazole, 2 -(P-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4 Thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) ) P-dialkylaminophenyl group-containing compounds such as pyrimidine. Of these, 4,4′-dialkylaminobenzophenone is most preferred.
The blending ratio of the sensitizing dye is 0 to 20% by weight, preferably 0.2 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total solid content of the composition of the present invention.

(D) Color Material The color material used for the color filter in the present invention is mainly a pigment, but is not particularly limited and is appropriately selected depending on the intended use of the color filter. Examples of the color material include organic pigments, inorganic pigments, dyes, natural pigments, and the like, but organic pigments are preferable from the viewpoint of heat resistance and light resistance.

  In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrone, perylene, diketopyrrolopyrrole, various inorganic pigments Is available.

  Specifically, for example, pigments having the following pigment numbers can be used. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).

Red colorant: C.I. I. Pigment Red (PR) 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 78, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276

Blue colorant: C.I. I. Pigment Blue (P.B.) 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79

Green colorant: C.I. I. Pigment Green (PG) 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55

Yellow colorant: C.I. I. Pigment Yellow (P.Y.) 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 73, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208

Orange colorant: C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79

Violet colorant: C.I. I. Pigment Violet (P.V.) 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50

Brown colorant: C.I. I. Pigment Brown 1, 6, 11, 22, 23, 24, 25, 27, 29, 30, 31, 33, 34, 35, 37, 39, 40, 41, 42, 43, 44, 45
Black colorant: C.I. I. Pigment Black 1, 31, 32
Of course, other colorants can also be used.

  Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow-11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Bread 17, C.I. I. Reactive Bread 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. 1. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Pat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C, 1. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. 1. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  In addition, as the colorant that can be used in the composition for a color filter of the present invention, inorganic colorants such as barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, carbon black and the like are used.

  These colorants are preferably used after being dispersed to an average particle size of 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less.

(E) Other components The color filter composition according to the present invention is further added with a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, a smoothing agent, a coating aid and other additives as necessary. be able to.

  As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0 to 3% by weight with respect to the total solid content of the composition.

  Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. The blending amount of these plasticizers is preferably in the range of 10% by weight or less with respect to the total solid content of the composition.

  Moreover, the composition for color filters of this invention can add suitably an adhesive improvement agent, an applicability improvement agent, a development improvement agent, etc. other than each said component.

  The color filter composition according to the present invention may be used by dissolving in a solvent in order to dissolve additives such as viscosity adjustment and photopolymerization initiation system. What is necessary is just to select a solvent suitably according to the structural component of a composition, such as (a) binder resin and (b) monomer.

  Examples of the solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, and apco #. 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylforme, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl alcohol Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl lopionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. Two or more of these solvents may be used in combination.

(F) Production of Color Filter Composition and Color Filter An example of the color filter composition according to the present invention and a method for producing a color filter using the composition will be described.

(F-1) Production of color filter composition First, a color material is dispersed and adjusted to an ink state. The dispersion treatment is performed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the color material is finely divided by the dispersion treatment, the transmittance of transmitted light is improved and the coating characteristics are improved.

  The dispersion treatment is preferably performed in a system in which a colorant and a solvent are appropriately combined with a binder resin having a dispersion function, a dispersant such as a surfactant, a dispersion aid, and the like. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.

  For example, when the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several millimeters. The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink (coloring material, solvent, dispersant), the size of the sand grinder, and the like, and therefore needs to be adjusted as appropriate.

  Next, the colored ink obtained by the above dispersion treatment is mixed with a binder resin, a monomer, a photopolymerization initiation system, and the like to obtain a uniform solution. In each step of dispersion treatment and mixing, fine dust is often mixed, and thus the obtained solution is preferably filtered with a filter or the like.

(F-2) Manufacture of color filter The color filter according to the present invention can be generally manufactured by forming pixel images of red, green and blue on a transparent substrate provided with a black matrix.

  The material of the transparent substrate is not particularly limited. Examples of the material include heat such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene, thermoplastic sheet of polycarbonate, polymethyl methacrylate, polysulfone, epoxy resin, unsaturated polyester resin, and poly (meth) acrylic resin. Examples thereof include curable plastic sheets and various glass plates. Among these, a glass plate and a heat resistant plastic are preferable from the viewpoint of heat resistance.

  The transparent substrate may be previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as a silane coupling agent and a urethane polymer in order to improve physical properties such as surface adhesion.

  The black matrix is formed on a transparent substrate using a metal thin film or a black matrix pigment dispersion.

  The black matrix using a metal thin film is formed of, for example, a chromium single layer or two layers of chromium and chromium oxide. In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Subsequently, a photosensitive film is formed thereon, and then the photosensitive film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form a resist image. Thereafter, the thin film is etched to form a black matrix.

  When the black matrix pigment dispersion is used, a black matrix is formed using a photosensitive resin composition containing a black color material. For example, carbon black, bone black, graphite, iron black, aniline black, cyanine black, red or the like appropriately selected from inorganic or organic pigments and dyes, or a plurality of black color materials such as titanium black A black matrix is formed using a photosensitive resin composition containing a black color material obtained by mixing green, blue, and the like, in the same manner as in the following method for forming red, green, and blue pixel images.

  A color filter composition containing a coloring material of one of red, green, and blue is applied on a transparent substrate provided with a black matrix and dried. Then, a photomask is placed on the composition, and the photomask A pixel image is formed through image exposure, development, and heat curing or photocuring as necessary to form a colored layer. This operation is performed for each of the three color filter compositions of red, green (that is, the color filter composition according to the present invention) and blue to form a color filter image.

  Application of the color filter composition can be performed by an application apparatus such as a spinner, a wire par, a flow coater, a die coater, a roll coater, or a spray.

  Drying after application may be performed using a hot plate, IR oven, convection oven, or the like. The higher the drying temperature, the better the adhesion to the transparent substrate. However, if the drying temperature is too high, the photopolymerization initiation system is decomposed, and thermal polymerization is easily induced to cause development failure. It is in the range of 150 ° C. The drying time ranges from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes.

  The film thickness of the color filter composition after drying is 0.5 to 3 μm, and preferably 1 to 2 μm.

  When the color filter composition according to the present invention uses a binder resin and an ethylenic compound in combination, and the binder resin is an acrylic resin having an ethylenic double bond and a carboxyl group in the side chain. Since this has very high sensitivity and high resolving power, it is preferable that an image can be formed by exposure and development without providing an oxygen blocking layer such as polyvinyl alcohol.

  The exposure light source applicable to the color filter composition according to the present invention is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. A lamp light source such as a low-pressure mercury lamp, a carbon arc, or a fluorescent lamp, or a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, or a semiconductor laser is used. When only a specific wavelength is used, an optical filter can be used.

  The color filter composition according to the present invention forms an image on a substrate by performing image exposure with such a light source and then developing with an organic solvent or an aqueous solution containing a surfactant and an alkali agent. be able to. This aqueous solution can further contain an organic solvent, a buffer, a dye or a pigment.

  Although there is no restriction | limiting in particular about the image development method, Usually, methods, such as immersion image development, spray image development, brush image development, and ultrasonic image development, are used at the image development temperature of 10-50 degreeC, Preferably 15-45 degreeC.

  Alkaline agents include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate Or organic amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, and tetraalkylammonium hydroxide, which can be used alone or in combination.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; and alkylbenzene sulfonic acids. Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids can be used.

  For example, isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like can be used as the organic solvent when used alone or in combination with an aqueous solution.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “parts” represents parts by weight.

(1-1) Production of High Contrast Filter Polymethylmethacrylate resin (binder resin for high contrast filter) based on a transparent biaxially stretched polyethylene terephthalate film (Mitsubishi Chemical Polyester Film Co., Ltd. PET film, thickness 175 μm) Applying 148 wt% of acrylic resin spherical beads with an average particle size of 22.3 μm to the 30 wt% toluene solution of Mitsubishi Rayon, Dianar BR-80) Then, the coating liquid was applied and dried by a bar coating method and uniformly applied, and then the solvent was dried to obtain a light diffusion layer made of transparent beads.

  Furthermore, on the opposite side of the formation of the light diffusing layer, spherical beads made of acrylic resin having an average particle diameter of 25 μm are made high with respect to a 30 wt% toluene solution of polymethyl methacrylate resin which is a binder resin for high contrast filters. A coating solution was prepared by adding 5 wt% with respect to the binder resin component for the contrast filter and further mixing pyrazole-based squarylium compounds represented by the formula (III-3) as shown in the following table. The coating liquid was applied and dried by a bar coating method, and after uniformly coating, the solvent was dried to obtain a high contrast filter on which a pigment dispersion layer was formed. The high contrast filter 1 is for use in the comparative example, and no dye is added.

  As a result of evaluating the high-contrast filter manufactured in this way on the light guide of the sidelight type backlight device, each high-contrast filter has the lens effect (front luminance improvement effect) by acrylic resin beads. And having high brightness in the front direction, it was confirmed that it is suitable as a high contrast filter used in a liquid crystal display device. Specifically, as a result of measuring the front luminance using a luminance measuring device (BM-7 manufactured by Topcom), if the front luminance directly above the light guide measured without a high contrast filter is 1, It was confirmed that the front luminance after providing the contrast filter 1 was 1.7 times. The high contrast filters 2 and 3 were 1.5 times and 1.45, respectively.

(1-2) White balance evaluation (1)
Using a Hitachi spectrophotometer U-3500, the transmittance is measured with the high contrast filter 1 as a reference, and color calculation is performed using the spectral characteristics of the CIE standard C light source and the spectral characteristics of the high contrast filters 2 and 3. It was. Table 16 shows the calculation results of chromaticity.

Thus, the high contrast filters 2 and 3 of Examples 1 and 2 have at least one of x and y larger than white (x, y) = (0.3, 0.3) when used alone. Observed in a reddish color.

(2) Manufacture of color filter (2-1) Manufacture of binder resin for color filter 20 parts of styrene / acrylic acid resin having an acid value of 200 and a weight average molecular weight of 5,000, 0.2 part of p-methoxyphenol, dodecyltrimethylammonium A flask was charged with 0.2 parts of chloride and 40 parts of propylene glycol monomethyl ether acetate, and 7.6 parts of (3,4-epoxycyclohexyl) methyl acrylate was added dropwise and reacted at a temperature of 100 ° C. for 30 hours. The reaction solution was reprecipitated in water and dried to obtain a resin. When neutralization titration with KOH was performed, the acid value of the resin was 80 mgKOH / g.

(2-2) Manufacture of resist solution Each component shown below was prepared at the following ratio and stirred with a stirrer until each component was completely dissolved to obtain a resist solution.
Binder resin solution 2.06 parts Dipentaerythritol hexaacrylate 0.21 part Photopolymerization initiation system 2- (2'-chlorophenyl) -4,5-diphenylimidazole 0.06 part 2-mercaptobenzothiazole 0.02 part・ 4,4′-bis (diethylamino) benzophenone 0.04 parts Solvent (propylene glycol monomethyl ether acetate) 5.41 parts Surfactant (FC-430 (manufactured by Sumitomo 3M)) 0.0003 parts

(2-3) Manufacture of red pixel 75 parts of propylene glycol monomethyl ether acetate, 17 parts of red pigment Pigment Red (PR) 254, 8 parts of urethane-based dispersion resin are mixed and stirred for 3 hours with a stirrer to obtain a solid content concentration A 25% by weight millbase was prepared. 500 parts of 0.5 mmφ zirconia beads were used for this mill base and subjected to a dispersion treatment for 3 hours at a peripheral speed of 10 m / s in a bead mill apparatus with a residence time. R. 254 dispersion ink (PR 254 ink) was obtained.
Pigment is changed to P.I. R. Except for the change to 177 R. A mill base was prepared with the same composition as that of H.254, and dispersion treatment was performed for 2 hours with a residence time under the same dispersion conditions. R. 177 dispersion ink (PR 177 ink) was obtained.

  The dispersion ink obtained as described above was dried under a light source combining a backlight having a relative light emission intensity distribution shown in FIG. 7 and the high contrast filters 1 to 3 produced in (1-1). The concentration of the above-mentioned pigment for realizing (x, y) = (0.640, 0.330) at a post film thickness of 2.0 μm was obtained by CCM (Computer Color Matching) calculation. And the compounding quantity of each dispersion ink for achieving the density | concentration of each pigment obtained as a calculation result was calculated, and the dispersion ink mixture was prepared. Table 17 shows the blending ratio of the pigments.

  To this dispersion ink mixture, the resist solution prepared in (2-2) is added so that the film thickness after drying is 2.0 μm, and a solvent (propylene glycol monomethyl) is added so that the final solid content concentration becomes 25%. Ether acetate) was added to obtain a red color filter composition.

The obtained color filter composition was applied and dried on a 10 cm × 10 cm glass substrate (AN635 manufactured by Asahi Glass Co., Ltd.) with a spin coater so that the dry film thickness was 2.0 μm. The entire surface of the substrate was irradiated with 200 mJ / cm ² of ultraviolet light, developed with an alkali developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare red pixel samples 1 to 3 for measurement.

(2-4) Production of green pixel G. Except for changing to 36, P.A. R. A mill base was prepared with the same composition as that of 254 ink, and dispersion treatment was performed for 1 hour with a residence time under the same dispersion conditions. G. 36 dispersion inks were obtained.
Pigment is changed to P.I. Y. Except for changing to 150. R. The mill base was adjusted with the same composition as that of 254 ink, and the dispersion treatment was performed for 2 hours with the residence time under the same dispersion conditions. Y. 150 dispersion inks were obtained.

  The dispersion ink obtained as described above was dried under a light source combining a backlight having a relative light emission intensity distribution shown in FIG. 7 and the high contrast filters 1 to 3 produced in (1-1). The concentration of the above-mentioned pigment for realizing (x, y) = (0.290, 0.600) at a post film thickness of 2.0 μm was obtained by CCM (Computer Color Matching) calculation. And the compounding quantity of each dispersion ink for achieving the density | concentration of each pigment obtained as a calculation result was calculated, and the dispersion ink mixture was prepared. Table 17 shows the blending ratio of the pigments.

  To this dispersion ink mixture, the resist solution prepared in (2-2) is added so that the film thickness after drying is 2.0 μm, and a solvent (propylene glycol monomethyl) is added so that the final solid content concentration becomes 25%. Ether acetate) was added to obtain a green color filter composition.

The obtained color filter composition was applied and dried on a 10 cm × 10 cm glass substrate (AN635 manufactured by Asahi Glass Co., Ltd.) with a spin coater so that the dry film thickness was 2.0 μm. The entire surface of the substrate was irradiated with 200 mJ / cm ² of ultraviolet light, developed with an alkaline developer, and then post-baked in an oven at 230 ° C. for 30 minutes to prepare green pixel samples 1 to 3 for measurement.

(2-5) Production of blue pixel G. P. 15 except for change to 15: 6. R. A mill base was prepared with the same composition as that of 254 ink, and dispersion treatment was performed for 1 hour with a residence time under the same dispersion conditions. G. A 15: 6 dispersion ink was obtained.
Pigment is changed to P.I. V. Except for the change to 23 R. The mill base was adjusted with the same composition as that of 254 ink, and the dispersion treatment was performed for 2 hours with the residence time under the same dispersion conditions. V. 23 dispersion inks were obtained.

  Next, under the light source combining the surface light source device having the relative light emission intensity distribution shown in FIG. 7 and the high contrast filters 1 to 3 created in (1-1), the chromaticity ( The concentration of the above-mentioned pigment for realizing x, y) = (0.150, 0.060) was determined by CCM (Computer Color Matching) calculation. And the compounding quantity of each dispersion ink for achieving the density | concentration of each pigment obtained as a calculation result was calculated, and the dispersion ink mixture was prepared. Table 17 shows the blending ratio of the pigments.

To this dispersion ink mixture, the resist solution prepared in (2-2) is added so that the film thickness after drying is 2.0 μm, and a solvent (propylene glycol monomethyl) is added so that the final solid content concentration becomes 25%. Ether acetate) was added to obtain a blue color filter composition.
The obtained color filter composition was applied and dried on a 10 cm × 10 cm glass substrate (AN635 manufactured by Asahi Glass Co., Ltd.) with a spin coater so that the dry film thickness was 2.0 μm. The entire surface of the substrate was irradiated with 200 mJ / cm ² of ultraviolet light, developed with an alkaline developer, and post-baked in an oven at 230 ° C. for 30 minutes to prepare blue pixel samples 1 to 3 for measurement.

(3-1) Evaluation of chromaticity Using a spectrophotometer U-3500 manufactured by Hitachi, Ltd., the transmittance of red, green and blue pixel samples obtained above with glass as a reference was measured, and the C light source of CIE standard was used. Color calculation was performed using spectral characteristics and spectral characteristics of the red, green, and blue pixel samples. Table 18 shows the calculation results of chromaticity.

(3-2) Evaluation of contrast It measured with the light luminance measuring apparatus (BM5 by Topcon). The method for evaluating the bias was performed by the following method. The polarized light of the two polarizing plates in a state where the produced high contrast filter and the pixel sample of each color of the corresponding color filter are sandwiched between two polarizing plates and irradiated from behind with a surface light source having the spectrum shown in FIG. The amount of transmitted light when the axes were parallel (when transmitting) and perpendicular (when blocked) was measured with a luminance measurement device (Topcom BM5), and the luminance during transmission / the luminance when blocked (contrast ratio) was calculated. The measurement results are shown in Table 18.
In Table 18, Comparative Example 1 corresponds to each color sample 1 for measurement, Example 1 corresponds to each color sample 2 for measurement, and Example 2 corresponds to each color sample 3 for measurement.

  Note that the color reproduction range of the set of red, green, and blue pixel samples obtained in this manner was 78% in terms of NTSC ratio. In a liquid crystal display device that develops color with a single color filter using a pigment without using a high-contrast filter, especially in a so-called high-color purity display with an NTSC ratio of 60% or more, it is difficult to improve contrast by improving the conventional color material However, according to the present invention, an improvement in contrast is realized even for such a high color purity display.

(3-3) White balance evaluation (2)
The transmittance of the high-contrast film, the transmittance of the red, green, and blue measuring pixel samples, and the spectral characteristics of the CIE standard C light source, measured using a Hitachi spectrophotometer U-3500 by the above method. Were used to calculate the chromaticity value and brightness of each color pixel sample and each high contrast film combination. Then, the chromaticity value (x, y) of the white balance was obtained from the chromaticity value and luminance value of each color. The calculation results are shown in Table 19.

Example 1
The high contrast filter 2 and each color pixel sample color-adjusted for the high contrast filter 2 were combined, and the chromaticity value and the luminance value were calculated.
(Example 2)
The high contrast filter 3 and each color pixel sample color-adjusted for the high contrast filter 3 were combined, and the chromaticity value and the luminance value were calculated.

(Comparative Example 1)
The high contrast filter 1 and each color pixel sample color-adjusted for the high contrast filter 1 were combined to calculate chromaticity values and luminance values.
(Comparative Example 2)
The color pixel samples adjusted for the high contrast filter 1 and the high contrast filter 2 were combined, and the chromaticity value and the luminance value were calculated.
(Comparative Example 3)
The color pixel samples color-adjusted for the high contrast filter 1 and the high contrast filter 3 were combined, and chromaticity values and luminance values were calculated.

  As apparent from Table 19, in Examples 1 and 2, which are combinations of high contrast filters 2 and 3 having a specific chromaticity and pixel samples having a chromaticity matched to the high contrast filter, It can be seen that a remarkable contrast improvement effect is obtained as compared with Comparative Example 1 having the same configuration. This effect is particularly noticeable in blue pixels.

  This is because the high-contrast filter having a specific chromaticity in Examples 1 and 2 described above has a characteristic of absorbing the blue-green sub-emission peak. Among the color pixel samples whose chromaticities are adjusted, particularly in the blue pixel sample, P.D. V. This is probably because the usage amount of 23 was reduced.

  In the same manner as in Examples 1 and 2, by producing a high contrast filter having a function of absorbing a sub-emission peak between green and red and a color filter corresponding thereto, green and red for the same purpose. Pigments used for pixels, such as P.I. R. 254, P.I. Y. 139, P.I. Y. Needless to say, it is possible to reduce the pigment by 150, and as a result, it is possible to improve the contrast of red and green.

It is a schematic block diagram of one Embodiment of the liquid crystal display device of this invention. It is a schematic sectional drawing of one embodiment of the light control film which concerns on this invention. (A), (b) is a schematic sectional drawing of the surface light source device which shows the function of a condensing film. It is a schematic sectional drawing of embodiment of the condensing film which has a pigment dispersion layer. It is a schematic sectional drawing of embodiment of the condensing film which has a pigment dispersion layer. (A), (b), (c) is an expansion perspective view of the condensing element currently formed in the condensing film. The figure which shows the emission spectrum of the 3 wavelength tube (cold cathode tube) used for the backlight of a general liquid crystal display device It is a general | schematic fragmentary sectional view which shows an example of the surface light source device of this invention. It is a general | schematic fragmentary sectional view which shows an example of the surface light source device of this invention. It is a schematic sectional drawing of embodiment of the condensing film which has a pigment dispersion layer.

Claims (9)

A color filter structure used in a liquid crystal display device,
A color filter formed as an aggregate of fine regions corresponding to red, green and blue pixels colored with pigments;
It is composed of a high contrast filter in which a dye having an absorption peak in the visible wavelength region is monomolecularly dispersed in a resin,
The white display chromaticity based on the chromaticity of the red, green and blue fine regions of the color filter, measured at a viewing angle of 2 degrees using a CIE standard C light source, is expressed as x, y in the CIE XYZ color system. X ≦ 0.35, y ≦ 0.38,
The chromaticity of the high-contrast filter, similarly measured using the C light source, is 0.30 ≦ x, y ≦ 0.45 in the x and y,
In addition, the chromaticity of the color filter structure measured in the same manner using the C light source is 0.25 ≦ x ≦ 0.35 and 0.28 ≦ y ≦ 0.38 in the x and y. A color filter structure characterized by. A liquid crystal display device having a surface light source device using a three-wavelength light source, a liquid crystal panel, and a high-contrast film and a color filter disposed in an optical path of light emitted from the light source,
The chromaticity at a viewing angle of 2 degrees when displaying white is 0.25 ≦ x, y ≦ 0.35 in x and y in the CIE XYZ color system,
A liquid crystal display device characterized in that chromaticities measured in the same manner when the light source is turned on with the color filter removed are 0.30 <x, y ≦ 0.45.   The chromaticity of the high-contrast filter measured at a viewing angle of 2 degrees using the C light source is 0.33 ≦ x ≦ 0.36 and 0.34 ≦ y ≦ 0.38 in the x and y. The color filter structure and color liquid crystal display device according to claim 1 or 2.   3. The color filter structure and color liquid crystal display device according to claim 1, wherein the dye used for the high contrast filter has a maximum absorption at a half-value width of 50 nm or less in a range from 455 nm to 540 nm.   The dye used for the high contrast filter is one or more of squarylium-based and / or porphyrin-based and / or tetraazaporphyrin-based and / or diazaporphyrin-based and / or azaporphyrin and / or dipyrromethene metal chelate-based compounds. The color filter structure and the color liquid crystal display device according to claim 1 or 2, wherein the colorant is a selected dye.   A liquid crystal display device comprising a surface light source device, a liquid crystal panel, and the color filter structure according to any one of claims 1 to 3.   The high contrast filter is formed by applying a coating liquid containing the dye on the surface of an optical system member used in the surface light source device, or by adding the dye to a material forming a base material of the optical system member. The liquid crystal display device according to claim 2, wherein the liquid crystal display device is formed as a part of the surface light source device.   The liquid crystal display device according to claim 7, wherein the optical system member is any one of a light diffusion sheet, a light collecting sheet, a polarizing film, a viewing angle widening film, a retardation film, and a light guide.   8. The color filter is provided in the liquid crystal panel, and the high contrast filter is provided in an optical path from a light emitting surface of the surface light source device to a visual recognition surface of the liquid crystal display device. Or the liquid crystal display device of Claim 8.

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