JP7173130B2 - Display device, manufacturing method thereof, liquid crystal aligning agent, and curable composition - Google Patents

Description

One embodiment of the present invention relates to a display device having a white light source and a color filter, a manufacturing method thereof, a liquid crystal aligning agent used for manufacturing an alignment film, and a curable composition used for manufacturing the color filter.

A liquid crystal display device is composed of a liquid crystal panel and a backlight. A backlight is a device that illuminates a liquid crystal panel from behind, and includes a diffusion plate, a light guide plate, and a light source. Light emitting diodes (LEDs) that emit red (R), green (G), and blue (B) colors, or white LEDs are used as light sources. For white LEDs, there is a single-chip system that combines a blue LED and a wavelength conversion material (phosphor), and a multi-chip system that uses LED chips that emit red (R), green (G), and blue (B) colors. It has been known. The single-chip method includes a method in which a blue LED and a wavelength conversion member that emits yellow light (yellow phosphor) are combined, a blue LED, a wavelength conversion member that emits red light (red phosphor), and a wavelength conversion member that emits green light. (green phosphor) is known.

A white LED as a light source is required to have both improved luminous efficiency and good color rendering properties. In order to achieve both luminous efficiency and color rendering properties, it is important to narrow the half width of the fluorescence spectrum of phosphors, and various phosphors have been developed. For example, K ₂ SiF ₆ :Mn (hereinafter also referred to as “KSF phosphor”) has been disclosed as a phosphor that emits red fluorescence (see Patent Document 1).

Among the three primary colors of light in a liquid crystal display device, green light is highly visible to the human eye and contributes significantly to the brightness of the image, so it is more important than the other two colors (red and blue). Are known. Therefore, the development of green phosphors (hereinafter also referred to as "green phosphors") with excellent fluorescence properties is also underway. As green phosphors, phosphors such as nitrides and oxynitrides are attracting attention, and in particular, β-sialon phosphors are being developed (see, for example, Patent Document 2).

A liquid crystal panel is provided with a color filter for a backlight using such a white LED as a light source. The color filter has a red (R) colored layer, a green (G) colored layer, and a blue (B) colored layer arranged corresponding to the arrangement of the pixels. Each colored layer has a property of transmitting light in a wavelength band corresponding to each color. For example, for white light emitted from a white LED, the blue colored layer transmits light in the blue wavelength band (435 nm to 480 nm), and the green colored layer transmits light in the green wavelength band (500 nm to 560 nm). The red colored layer has the property of transmitting light in the wavelength band of red light (610 nm to 750 nm). A liquid crystal display device displays a full-color image by combining a white light source and a color filter having such colored layers.

In liquid crystal display devices that display full-color images, such as liquid crystal televisions, color reproducibility is an important parameter as an indicator of image quality. For example, as an index of color reproducibility, a liquid crystal display device with an increased NTSC ratio has been disclosed (see Patent Document 3).

JP 2012-224536 A JP 2007-145919 A Japanese Patent Application Laid-Open No. 2004-163902

Color reproducibility can be improved by narrowing the spectral width of light corresponding to each of blue (B), green (G), and red (R) emitted through the color filter. On the other hand, the wavelength 555 nm, which has the highest luminosity, is cut off from the light from the white light source, and the spectrum width narrows, resulting in a decrease in the amount of transmitted light and a decrease in luminance.

Therefore, rather than simply increasing the color gamut, considering a combination of a white LED light source and a color filter that can reliably cover a specific chromaticity point is considered more suitable for improving image quality. For example, by combining a white LED light source with a color filter that can reliably cover a specific chromaticity point, it is conceivable to improve color reproducibility and suppress a decrease in luminance. In this case, it is considered effective to change the colorant used in the color filter from an organic pigment to an organic dye, a colorant containing an organic pigment, and an organic dye. However, the heat resistance of organic dyes is lower than that of organic pigments, and there is a problem that the organic dyes are thermally decomposed by the heat treatment required in the manufacturing process of the liquid crystal display device, thereby degrading the color characteristics.

（式（１）中、ｍ、ａ、ｂ、ｃは、各々独立に、０＜ｍ≦０．２、１．６≦ａ≦２．４、ｍ＋ｂ＝１、４．８≦ｃ≦７．２を満たす。）

（式（２）中、ａ、ｂ、ｃ、ｄ、ｅは、各々、０＜ａ≦０．２、５．６＜ｂ≦５．９９、０．０１≦ｃ＜０．４、０．０１≦ｄ＜０．４、７．６＜ｅ≦７．９９を満たす。）A display device according to an embodiment of the present invention includes a first white light source including a blue light source, a red phosphor having a composition represented by the following formula (1), and a green phosphor having a composition represented by the following formula (2). or a second white light source containing a blue light source, a green light source, and a red phosphor having a composition represented by the following formula (1); a red pixel, a green pixel, and a blue pixel; a display panel including a color filter having a red colored layer, a green colored layer arranged corresponding to the green pixels, and a blue colored layer arranged corresponding to the blue pixels; , or the chromaticity point of red light emitted from the second white light source and obtained by transmitting through the red colored layer, the chromaticity point of green light obtained by transmitting through the green colored layer, and the chromaticity point of green light obtained by transmitting through the blue colored layer The chromaticity coordinates of the CIE color system calculated from the chromaticity point of the blue light obtained by
Rx=0.035 cos(2πθ)+0.690,
Ry=0.035 sin(2πθ)+0.295,
Gx=0.055 cos(2πθ)+0.185,
Gy=0.055 sin(2πθ)+0.760,
Bx=0.030 cos(2πθ)+0.145,
By=0.030 sin(2πθ)+0.055
(However, θ represents a numerical value of 0 or more and less than 1.).

(In formula (1), m, a, b, and c are each independently 0<m≦0.2, 1.6≦a≦2.4, m+b=1, 4.8≦c≦7. 2.)

(In formula (2), a, b, c, d, and e are 0<a≦0.2, 5.6<b≦5.99, 0.01≦c<0.4, 0.01≦c<0.4, and 0.6<b≦5.99, respectively. 01≦d<0.4 and 7.6<e≦7.99 are satisfied.)

A method of manufacturing a display device according to an embodiment of the present invention includes steps of forming an array substrate provided with pixel electrodes respectively corresponding to red pixels, green pixels, and blue pixels; forming a counter substrate provided with a color filter having a red colored layer arranged corresponding to a green pixel, a green colored layer arranged corresponding to a green pixel, and a blue colored layer arranged corresponding to a blue pixel; , and a step of forming a coating film of a liquid crystal aligning agent on at least one of the opposing substrate, and baking the coating film of the liquid crystal aligning agent alignment agent at a temperature range of 80 ° C. or more and 150 ° C. or less to form an alignment film. and

According to the display device according to one embodiment of the present invention, either a white light source including a blue LED light source, a red phosphor, and a green phosphor, or a white light source including a blue LED light source, a green LED light source, and a red phosphor is used. Color reproducibility can be improved by combining a white light source and a color filter that can reliably cover a specific chromaticity point.

1 shows an exploded perspective view of a liquid crystal display device according to an embodiment of the present invention; FIG. 1 shows a cross-sectional view of a configuration of a main part of a liquid crystal display device according to an embodiment of the present invention; 1 shows the configuration of an edge-light type backlight used in a liquid crystal display device according to an embodiment of the present invention. 1 shows the configuration of a direct type backlight used in a liquid crystal display device according to an embodiment of the present invention. An example in which the white light source used for the backlight of the liquid crystal display device according to one embodiment of the present invention is composed of one monochromatic light source is shown. An example in which a white light source in a backlight of a liquid crystal display device according to an embodiment of the present invention is composed of a plurality of monochromatic light sources is shown. 1 shows a cross-sectional structure of a pixel portion of a display panel that constitutes a liquid crystal display device according to an embodiment of the present invention; 1 shows a cross-sectional structure of a pixel portion of a display panel that constitutes a liquid crystal display device according to an embodiment of the present invention; FIG. 10 is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming a switching element; FIG. 4A is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming an interlayer insulating film; FIG. 4A is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming a pixel electrode; FIG. 10 is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming a photospacer and an alignment film; FIG. 4A is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming a color filter; FIG. 4A is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming a protective film; FIG. 4A is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of forming an alignment film; FIG. 4 is a cross-sectional view illustrating a method of manufacturing a liquid crystal display device according to an embodiment of the present invention, showing a step of bonding an array substrate and a counter substrate to form a liquid crystal layer.

An embodiment of the present invention will be described with reference to the drawings and the like. However, the present invention can be implemented in many different aspects and should not be construed as being limited to the description of the embodiments exemplified below. In order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example and limits the interpretation of the present invention. not a thing In addition, in this specification and each figure, the same reference numerals or similar reference numerals (a, b, etc. are simply added after the number) are attached to the same elements as those described above with respect to the previous figures. and detailed description may be omitted as appropriate.

In this specification, the terms "upper", "above", and "upper surface" refer to the side on which the display panel overlaid on the backlight is arranged, with the position of the backlight as a reference for the sake of convenience. Also, the side on which the backlight is arranged as viewed from the display panel is referred to as "lower", "downward", and "lower surface". In addition, "above", "above" and "upper surface" include the case of being in contact with the object and the case of being positioned above the object. shall mean the opposite case.

1. Liquid Crystal Display Device An overall configuration of a liquid crystal display device 100 according to an embodiment of the present invention will be described.

1-1. Overall Structure of Liquid Crystal Display Device FIG. 1 shows an exploded perspective view of a liquid crystal display device 100 according to an embodiment of the present invention. The liquid crystal display device 100 has a display panel 102 and a backlight 104 . The liquid crystal display device 100 illustrated in FIG. 1 is of a transmissive type, and a backlight 104 is arranged behind the display panel 102 .

For example, a frame-shaped front frame 132 is provided on the front surface of the display panel 102 , and a box-shaped chassis 146 is arranged on the rear surface of the backlight 104 . Although not shown, polarizing plates are arranged on the front side and the rear side of the display panel 102, respectively.

The backlight 104 includes a white light source 106 , a light guide plate 108 , an optical film 110 and a reflecting member 109 . The white light source 106 shown in FIG. 1 is arranged on the side surface of the light guide plate 108 . The backlight 104 is roughly classified into an edge light type and a direct type, and the backlight according to an embodiment of the present invention can be realized by both types. FIG. 1 shows an edge-lit backlight 104a. The edge-light type backlight 104 a includes a white light source 106 , a light guide plate 108 and an optical film 110 . The edge-light type backlight 104a has a function of illuminating the display panel 102 from behind by guiding the white light emitted from the white light source 106 through the light guide plate 108 and diffusing it through the optical film 110 .

The backlight 104 may be provided with a heat dissipation member 144 . The heat dissipation member 144 is provided so as to be in contact with the white light source 106 and the chassis 146 and has a function of diffusing heat generated by the white light source 106 to the chassis 146 . The reflecting member 109 is a plate-like or film-like member having a specular or satin-finished surface, and is processed so that light is specularly reflected or diffusely reflected on the surface of the light guide plate 108 . The light guide plate 108 is a rectangular plate-like member, and is made of resin or the like that is colorless and transparent in the visible light region.

The optical film 110 is provided to efficiently irradiate the display panel 102 with the light emitted from the light guide plate 108 . The optical film 110 may be composed of multiple films. For example, the optical film 110 may include a diffusion sheet 136, a prism sheet 138, a reflective polarizing sheet 142, and the like. The diffusion sheet 136 has a function of diffusing light to improve in-plane uniformity of the backlight 104, and the prism sheet 138 has a function of condensing light to improve in-plane brightness. The sheet 142 has a function of increasing the utilization efficiency of the light emitted from the backlight 104 by reflecting and reusing the light component that does not pass through the polarizing plate 112a provided on the rear rear side of the display panel 102. is doing. The optical film 110 is not limited to these sheets, and other members may be used. The casing frame 134 is provided to sandwich the optical film 110 and the light guide plate 108 and fix the backlight 104 and the display panel 102 . The display panel 102 is firmly fixed by the front frame 132 and the casing frame 134 .

1-2. Structure of Main Part of Liquid Crystal Display Device FIG. 2 is a cross-sectional view showing the structure of the main part of the liquid crystal display device 100 according to one embodiment of the present invention. The display panel 102 includes an array substrate 114 , a counter substrate 116 and a liquid crystal layer 118 . The array substrate 114 and the counter substrate 116 are arranged with a gap therebetween with a spacer 128 interposed therebetween, and fixed with a sealing agent 130 . A liquid crystal layer 118 is arranged in a gap between the array substrate 114 and the counter substrate 116 . A pair of polarizing plates 112 a and 112 b are arranged with respect to the display panel 102 with an array substrate 114 and a counter substrate 116 interposed therebetween.

A circuit element layer 120 is provided on the array substrate 114 . Although not shown in detail in FIG. 2, the circuit element layer 120 is provided with switching elements and pixel electrodes electrically connected to the switching elements. A color filter 122 is provided on the counter substrate 116 . Color filter 122 includes a colored layer 124 . The colored layer 124 is provided corresponding to each color of red (R), green (G), and blue (B). For example, the red colored layer 124r has at least one transmission spectrum peak in the red wavelength band (610 nm to 750 nm) and has the property of transmitting red light, and the green colored layer 124g has the characteristic of transmitting red light. 560 nm) and has a characteristic of transmitting green light, and the blue colored layer 124b includes at least one transmission spectrum peak in the blue wavelength band (435 nm to 480 nm) and transmits blue light. It has the property of being permeable.

The color filter 122 may include colored layers corresponding to other colors in addition to the colored layers 124 (the red colored layer 124r, the green colored layer 124g, and the blue colored layer 124b). For example, the color filter 122 may include a yellow colored layer having a transmission spectrum peak in the yellow wavelength band (580 nm to 595 nm). Further, the color filter 122 may be provided with a light shielding layer 126 so as to fill the space between the colored layers 124 .

When the liquid crystal layer 118 is in IPS (In-Plane Switching) mode or VA (Vertical Aligned) mode, the polarizing plates 112a and 112b are arranged in crossed Nicols. In the IPS mode, the light emitted from the backlight 104 is linearly polarized by the polarizing plate 112a, and when an electric field is applied to the liquid crystal layer 118 and the liquid crystal molecules are rotated by 90 degrees, the light is emitted through the polarizing plate 112b. . At this time, the white light is filtered by the colored layer 124 of the color filter 122 , and light in a predetermined wavelength band is emitted from the display panel 102 .

Thus, the liquid crystal display device 100 modulates the light emitted from the backlight 104 by the polarizing plates 112a and 112b, the liquid crystal layer 118, and the color filter 122 (colored layer 124), and the light emitted from the display panel 102 is modulated. It controls the presence or absence of , and the color (wavelength band) of the emitted light. By performing such control for each pixel, the liquid crystal display device 100 displays characters, still images, and moving images. Therefore, in order to improve the color reproducibility of the liquid crystal display device 100, simply optimizing the color filters is not sufficient. It is considered preferable to consider compatibility with the spectrum. In the following description, based on such a viewpoint, details of the backlight and the white light source used in the liquid crystal display device of the present embodiment and the display panel provided with the color filter will be described in detail.

1-3. Backlight Structure FIG. 3A shows a cross-sectional view of the structure of an edge-lit backlight 104a. The edge-light type backlight 104 a includes a white light source 106 , a light guide plate 108 , an optical film 110 and a reflective member 109 .

A white light source 106 is arranged on a side surface of the light guide plate 108 . The white light source 106 a includes a monochromatic light source 148 and a wavelength conversion layer 150 inside a package 158 . The white light source 106a is configured such that part of the light emitted from the monochromatic light source 148 is wavelength-converted by the wavelength conversion layer 150 to emit white light.

The light emitted from the white light source 106 and incident on the inside of the light guide plate 108 is reflected by the reflecting member 109 provided on the back side of the light guide plate 108 in the course of traveling while being totally reflected, and the component whose angle of reflection is smaller than the angle of total reflection. of light is emitted from the surface of the light guide plate 108 . The surface of the reflecting member 109 may be provided with uneven portions (reflecting dots) so as to scatter light. Further, a diffusion sheet 136, a prism sheet 138, and a reflective polarizing sheet 142 may be provided as the optical film 110 on the light exit surface of the light guide plate 108 so as to form a uniform surface light source. In the backlight 104a, due to the action of the optical film 110, unevenness in brightness within the plane is eliminated, and brightness within the plane is improved.

FIG. 3B shows a cross-sectional structure of a direct type backlight 104b. The direct type backlight 104b includes a plurality of monochromatic light sources 148 (monochromatic light sources 148a to 148c) spaced apart in a plane, and a plurality of wavelength converters provided to cover each of the plurality of monochromatic light sources 148. It includes a layer 150 (wavelength conversion layers 150a-150c) and an optical film 110. FIG. The direct type backlight 104 b forms the white light source 106 with the monochromatic light source 148 and the wavelength conversion layer 150 . In the direct type backlight 104b, the white light sources 106 are discretely provided as point light sources. Although no light guide plate is used in the direct type, the white light from the white light source 106 which is discrete in a point form is diffused planarly by the diffusion plate 140, the optical film 110 composed of the diffusion sheet 136, the prism sheet 138, and the like. be done. The direct type backlight 140 b forms a surface light source with the optical film 110 .

A light emitting diode (LED) is used as the monochromatic light source 148 used in the white light source 106 shown in FIGS. 3A and 3B. As the light emitting diode, it is preferable to use, for example, a blue light emitting diode. Also, the wavelength conversion layer 150 preferably contains a coloring material that absorbs blue light and converts it into red light, and a coloring material that absorbs blue light and converts it into green light. Details of the white light source 106 including such members will be described below.

1-4. White Light Source FIG. 4A shows a cross-sectional structure of white light source 106a including blue light source 148a and wavelength conversion layer 150a. A so-called blue light emitting diode is used for the blue light source 148a, and for example, an InGaN light emitting diode, a GaN light emitting diode, or the like is used. An InGaN light emitting diode emits blue light having an emission peak in a wavelength range of 410 nm to 500 nm, and a GaN light emitting diode emits near-ultraviolet light having an emission peak in a wavelength range of 350 nm to 410 nm.

Wavelength conversion layer 150 a includes red phosphor 152 and green phosphor 154 . The wavelength conversion layer 150a has these phosphors dispersed in a resin material. The red phosphor 152 is a coloring material that absorbs the blue light (or near-ultraviolet light) emitted from the blue light source 148a and fluoresces the red light. or near-ultraviolet light) and fluoresces green light.

White light source 106 a emits light from blue light source 148 a , part of the emitted light is absorbed by red phosphor 152 and color-converted into red light, and the other part is absorbed by green phosphor 154 . Color-converted to green light. Therefore, white light source 106a can emit white light by including red phosphor 152 and green phosphor 154 in a predetermined ratio in wavelength conversion layer 150a.

The blue light source 148a and the wavelength conversion layer 150a are arranged in a concave portion formed by a package 158 having an opening with an upward inclined surface and a bottom plate 156 having a lead frame 160 provided thereon. The blue light source 148 a is placed on the bottom of the concave surface and electrically connected with the lead frame 160 at the bottom of the package 158 . The inclined surface at the opening of the package 158 serves as a reflecting surface, and is configured to reflect oblique light emitted from the blue light source 148a and emit the light to the outside. The wavelength conversion layer 150a is provided so as to fill the concave portion and embed the blue light source 148a. A cover glass 162 may be provided as a protective member at the light exit port.

FIG. 4B shows a cross-sectional structure of white light source 106b including blue light source 148a and green light source 148b and wavelength conversion layer 150b. A blue light emitting diode is used for the blue light source 148a, and a green light emitting diode is used for the green light source 148b. GaP light-emitting diodes and InGaN light-emitting diodes, for example, are used as green light-emitting diodes. GaP light emitting diodes have an emission center wavelength of 555 nm, and InGaN light emitting diodes have an emission center wavelength of 520 nm.

Wavelength conversion layer 150 b includes red phosphor 152 . The wavelength conversion layer 150b has these phosphors dispersed in a resin material. The red phosphor 152 is a coloring material that absorbs the blue light emitted from the blue light source 148a and the green light emitted from the green light source 148b and fluoresces the red light.

White light source 106b emits blue light from blue light source 148a and green light from green light source 148b, and part of the emitted light is absorbed by red phosphor 152 and converted into red light. White light source 106b can emit white light by including red phosphor 152 at a predetermined ratio in wavelength conversion layer 150b.

The white light source 106a and the wavelength conversion layer 150b contain a predetermined color material as a phosphor, so that the spectrum of the light emitted by fluorescence can be appropriately adjusted. For example, the emission spectrum of the fluorescent material can be adjusted to match the transmission spectrum of the color filters.

2. Backlight This section exemplifies the fluorescent material used for the white light source 106 constituting the backlight 104 used in the liquid crystal display device 100 according to the present embodiment.

2-1. Red phosphor For example, a KSF phosphor containing potassium (K), silicon (Si), fluorine (F), and manganese (Mn) may be used. 09131 publication.

In this embodiment, the red phosphor includes a crystal having a composition represented by the following general formula (1).

（式（１）中、ｍ、ａ、ｂ、ｃは、各々独立に、０＜ｍ≦０．２、１．６≦ａ≦２．４、ｍ＋ｂ＝１、４．８≦ｃ≦７．２を満たす。）

(In formula (1), m, a, b, and c are each independently 0<m≦0.2, 1.6≦a≦2.4, m+b=1, 4.8≦c≦7. 2.)

In Formula (1), Mn represents manganese. Mn is other activating elements such as europium (Eu), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium ( Sm), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb). In formula (1), m represents the content of Mn, the range is usually 0 < m ≤ 0.2, the lower limit is preferably 0.01, more preferably 0.02, and the upper limit The value is preferably 0.15, more preferably 0.1. Within this range, concentration quenching is less likely to occur, and heterogeneous phases exhibiting chemical compositions other than the phosphor used in one embodiment of the present invention are less likely to occur, which is preferable in terms of good emission characteristics.

In formula (1), K represents potassium. K is partially substituted with other Group 1 elements of the periodic table, such as alkali metals such as lithium (Li), sodium (Na), rubidium (Rb), cesium (Cs), and francium (Fr). may In formula (1), a represents the content of K, the range is usually 1.6 ≤ a ≤ 2.4, the lower limit is preferably 1.8, more preferably 1.85, The upper limit is preferably 2.2, more preferably 2.15.

In formula (1), Si represents silicon. Si may be partially substituted with other tetravalent elements such as germanium (Ge), tin (Sn), titanium (Ti) and zirconium (Zr). In formula (1), b represents the content of silicon. The mutual relationship between m representing the Mn content and b representing the silicon content usually satisfies m+b=1.

In formula (1), F represents fluorine. F may be partially substituted with other halogen elements such as Cl (chlorine), Br (bromine), I (iodine), and oxygen. In formula (1), c represents the content of fluorine, the range is usually 4.8 ≤ c ≤ 7.2, the lower limit is preferably 5.2, more preferably 5.6, The upper limit is preferably 6.8, more preferably 6.4. When both are within the above range, the effects of the present invention are preferably obtained, which is preferable.

2-2. Characteristics of Red Phosphor The red phosphor used in the present embodiment preferably has the following characteristics when excited with light having a peak wavelength of 455 nm and measuring the emission spectrum. That is, the peak wavelength λp (nm) in the emission spectrum is usually 600 nm or more, preferably 610 nm or more, more preferably 620 nm or more, and usually 650 nm or less. It is preferable that the emission spectrum is within such a range in terms of having suitable orange to red emission.

In the red phosphor according to the present embodiment, the half width of the emission peak in the above emission spectrum is usually less than 50 nm, especially 40 nm or less, further 20 nm or less, particularly 10 nm or less, usually 1 nm or more. preferable. If the half width of the emission spectrum is too wide, the color purity may decrease, and if it is too narrow, the emission intensity may decrease.

A xenon light source, for example, can be used to excite the phosphor with light having a peak wavelength in the blue band or the near-ultraviolet band. Further, the emission spectrum of the red phosphor according to this embodiment can be measured using, for example, a fluorescence spectrophotometer (model number: F-4500, manufactured by Hitachi Ltd.). The emission peak wavelength and the half width of the emission peak can be calculated from the obtained emission spectrum.

2-3. Green Phosphor A β-sialon phosphor can be used as the green phosphor. A β-sialon phosphor is disclosed in, for example, Japanese Patent Application Laid-Open No. 2016-132724.

In the present embodiment, the β-sialon phosphor is preferably a phosphor represented by the following formula (2) and has a La content of 10 ppm or more and 2000 ppm or less.

（式（２）中、ａ、ｂ、ｃ、ｄ、ｅは、各々、０＜ａ≦０．２、５．６＜ｂ≦５．９９、０．０１≦ｃ＜０．４、０．０１≦ｄ＜０．４、７．６＜ｅ≦７．９９を満たす。）

(In formula (2), a, b, c, d, and e are 0<a≦0.2, 5.6<b≦5.99, 0.01≦c<0.4, 0.01≦c<0.4, and 0.6<b≦5.99, respectively. 01≦d<0.4 and 7.6<e≦7.99 are satisfied.)

In formula (2), Eu represents europium. Eu is partially combined with other activating elements such as manganese (Mn), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), terbium (Tb), dysprosium (Dy), holmium ( Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and the like. In formula (2), a represents the content of Eu, the range is usually 0 < a ≤ 0.2, the lower limit is preferably 0.0001, more preferably 0.001, or The upper limit is preferably 0.15, more preferably 0.1, particularly preferably 0.08.

In formula (2), Si represents silicon. Si may be partially substituted with other tetravalent elements such as germanium (Ge), tin (Sn), titanium (Ti), zirconium (Zr), and hafnium (Hf). In formula (2), b represents the content of Si, the range is usually 5.6 < b ≤ 5.99, the lower limit is preferably 5.7, and the upper limit is preferably is 5.97.

In formula (2), Al represents aluminum. Al is other trivalent elements such as boron (B), gallium (Ga), indium (In), scandium (Sc), yttrium (Y), lanthanum (La), gadolinium (Gd), lutetium (Lu ), etc., may be partially substituted. In formula (2), c represents the content of Al, the range is usually 0.01 ≤ c < 0.4, the lower limit is preferably 0.03, and the upper limit is preferably 0.3.

In Formula (2), O represents an oxygen element and N represents a nitrogen element. O or N may partially contain other elements such as halogen atoms (fluorine (F), chlorine (Cl), bromine (Br), iodine (I)) and the like. Halogen atoms may be mixed as impurities in the raw material metal, or may be introduced during the manufacturing process such as the pulverization process or the nitriding process. may be lost. In formula (2), d represents the content of O, the range is usually 0.01 ≤ d < 0.4, the lower limit is preferably 0.03, and the upper limit is preferably 0.3. In formula (2), e represents the content of N, the range is usually 7.6 < e ≤ 7.99, the lower limit is preferably 7.7, and the upper limit is preferably 7.77.

In the green phosphor according to the present embodiment, it is preferable that the content of the constituent elements is within the above-described range, because the obtained phosphor has good emission characteristics.

The green phosphor according to this embodiment may contain La. The La content is usually 10 ppm or more and 2000 ppm or less, and its upper limit is preferably 1500 ppm or less, more preferably 1000 ppm or less. Within such a range, it is preferable in that the luminance of the phosphor to be obtained is excellent.

2-4. Characteristics of Green Phosphor The β-sialon phosphor according to the present embodiment is excited by light having a wavelength of 300 nm or more and 500 nm or less, and its emission peak wavelength is usually 500 nm or more and 560 nm or less. It is preferably 510 nm or more, preferably 520 nm or more, and the upper limit is preferably 550 nm or less.

3. Structure of Display Panel In this section, the structures of the array substrate 114 and the counter substrate 116 that constitute the display panel 102 will be described in detail.

3-1. Structure of Pixel FIG. 5 shows a cross-sectional structure of the pixel portion 164 a of the display panel 102 . FIG. 5 schematically shows a cross-sectional structure of part of the pixel section 164, showing a mode in which a pixel 166r corresponding to red, a pixel 166g corresponding to green, and a pixel 166b corresponding to blue are arranged. In the pixel section 164, the array substrate 114 and the counter substrate 116 are arranged facing each other with a gap therebetween, and the liquid crystal layer 118 is provided in the gap. The array substrate 114 is provided with a circuit element layer 120 including switching elements 168 , pixel electrodes 170 , an insulating film 184 between the switching elements 168 and the pixel electrodes 170 , and an organic interlayer insulating film 180 . A color filter 122 including a colored layer 124 and a light shielding layer 126 is provided on the counter substrate 116 .

Specifically, on the array substrate 114 side, a switching element 168r of a red pixel 166r and a pixel electrode 170r electrically connected to the switching element 168r are provided. Similarly, the green pixel 166b is provided with a switching element 168g and a pixel electrode 170g electrically connected to the switching element 168g. A pixel electrode 170b is provided. Between the switching elements 168r, 168g, 168b and the pixel electrodes 170r, 170g, 170b, an insulating film 184 that also serves as a protective film and an organic interlayer insulating film 180 that also serves as a planarizing film are provided.

The switching element 168 is formed by a thin film transistor. In the thin film transistor, a source region, a drain region, and a channel formation region are formed in a semiconductor film with a thickness of 20 nm to 200 nm formed over a base insulating film 172, and a gate electrode 178 is insulated from the semiconductor film 174 by a gate insulating film 176. It has the structure of an insulated gate field effect transistor. As the semiconductor film, in addition to silicon materials such as amorphous silicon and polysilicon, metal oxides (oxide semiconductors) exhibiting semiconductor characteristics are used.

FIG. 5 shows a pixel structure corresponding to the IPS system. That is, FIG. 5 shows a configuration in which a common electrode 171r fixed at a constant potential is provided with an insulating film 182 interposed between the pixel electrodes 170r, and a horizontal electric field is applied to the liquid crystal layer 118. FIG. Similarly, in the green pixel 166g, a common electrode 171g is provided across the insulating film 182 for the pixel electrode 170g, and in the green pixel 166b, the common electrode 171b is provided across the insulating film 182 for the pixel electrode 170b. . It should be noted that the present invention is not limited to the IPS system, and can be applied to various liquid crystal modes such as the VA (Vertical Alignment) system, the FFS (Fringe Field Switching) system, and the TN (Twisted Nematic) system.

A color filter 122 is provided on the counter substrate 116 . The color filter 122 has a red colored layer 124r provided in a region corresponding to the red pixel 166r, a green colored layer 124g provided in a region corresponding to the green pixel 166g, and a blue colored layer 124b provided in a region corresponding to the blue pixel 166b. be provided. A light shielding layer 126 is provided between each region of the red colored layer 124r, the green colored layer 124g, and the blue colored layer 124b.

The red colored layer 124r contains a red coloring material, the green colored layer 124g contains a green coloring material, and the blue colored layer 124b contains a blue coloring material. Each of the colored layers 124 contains a coloring material at a concentration of 10% by mass or more and 50% by mass or less with respect to the mass of the resin used as the binder. In this embodiment, a pigment, a dye, or a combination thereof is used as the coloring material used for the colored layer 124 . The coloring material contained in the red colored layer 124r includes at least one selected from diketopyrrolopyrrole, anthraquinone, azo, isoindoline, methine, xanthene, and dioxazine. The coloring material contained in the green colored layer 124g includes phthalocyanine, azo , quinophthalone, coumarin, merocyanine, squarylium, and azomethine, and the coloring material contained in the blue colored layer 124b includes at least one selected from phthalocyanine, dioxazine, triarylmethane, xanthene, and anthraquinone.

A protective film 186 may be provided on the top surface of the color filter 122 (the surface on the liquid crystal layer 118 side). The protective film 186 is formed from a curable composition containing resin materials such as acrylic resin and epoxy resin. The unevenness formed by the color filter 122 is buried by the protective film 186 to form a flat surface. An alignment film 188b is provided on the upper surface of the protective film 186 (the surface on the liquid crystal layer 118 side). Since the alignment film 188b is provided on the flat surface formed by the protective film 186, it is possible to control the alignment of the liquid crystal and prevent the alignment disorder.

An alignment film 188a is similarly provided on the array substrate 114 side. The alignment film 188 is provided for regularly aligning the liquid crystal molecules. The alignment film 188 is processed so that the liquid crystal molecules are aligned in a predetermined direction by applying a physical treatment such as rubbing or a photo-alignment technique. In this embodiment, an alignment film containing polyamic acid and a polyamic acid derivative is used as the alignment film 188, and in a low-temperature firing process of 200° C. or less, an alignment agent containing a specific cross-linking agent or a specific solvent, and an aromatic An alignment film 188 containing at least one type of polymer selected from the group consisting of hydrocarbon group-containing styrenic polymers, (meth)acrylic polymers, polysiloxanes, polyamic acids and polyamic acid derivatives can be used.

A spacer 128 is arranged between the array substrate 114 and the opposing substrate 116 so that the liquid crystal layer 118 is held with a constant thickness. A columnar spacer or a bead spacer can be used as the spacer 128 . The columnar spacers 128 are formed at specific positions using a photosensitive resin composition by exposure and development by photolithography. For example, the columnar spacers 128 can be provided in alignment with contact holes formed in the organic interlayer insulating film 180 . Such columnar spacers 128 define the thickness (cell gap) of the liquid crystal layer 118 and are formed at a height of 3 μm to 10 μm from the upper surface of the pixel electrode.

FIG. 6 shows an aspect of a pixel portion 164b in which colored layers 124r, 124g, and 124b are provided on the array substrate 114 side. The colored layers 124r, 124g, and 124b are provided between the insulating film 184 provided on the switching elements 168r, 168g, and 168b and the organic interlayer insulating film 180. As shown in FIG. Colored layers 124r, 124g, and 124b are provided to embed switching elements 168r, 168g, and 168b, respectively. Opposite substrate 116 is provided with light shielding layers 126r, 126g and 126b in regions overlapping with switching elements 168r, 168g and 168b. By shielding these regions from light, the switching elements 168r, 168g, and 168b are shielded from light, and light can be transmitted through regions where the thickness of the colored layers 124r, 124g, and 124b is uniform.

3-2. About the chromaticity coordinates of the CIE color system,
The CIE color system is a method of expressing colors that has been approved as a standard color system by the CIE (Commission Internationale d'Eclairage). , Ry), (Gx, Gy), and (Bx, By), the chromaticity point of the red light obtained by transmitting the LED white light source through the red colored layer, the chromaticity point of the red light obtained by transmitting the LED white light source through the green colored layer, The chromaticity coordinates are shown by the following formula of the CIE color system calculated from the chromaticity point of the obtained green light and the chromaticity point of the blue light obtained by the LED white light source passing through the blue colored layer.

Rx=0.035 cos(2πθ)+0.690,
Ry=0.035 sin(2πθ)+0.295,
Gx=0.055 cos(2πθ)+0.185,
Gy=0.055 sin(2πθ)+0.760,
Bx=0.030 cos(2πθ)+0.145,
By=0.030 sin(2πθ)+0.055
However, θ represents a numerical value of 0 or more and less than 1.

A color filter and a white LED light source within this chromaticity coordinate range are preferable because the color reproducibility of the color liquid crystal display device is enhanced.

3-3. Coloring material (coloring material)
As the coloring material, the coloring material contained in the red colored layer is at least one selected from diketopyrrolopyrrole, anthraquinone, azo, isoindoline, methine, xanthene, and dioxazine, and the coloring material contained in the green colored layer is It is at least one selected from phthalocyanine, azo, quinophthalone, coumarin, merocyanine, squarylium, and azomethine, and the coloring material contained in the blue colored layer is at least one selected from phthalocyanine, dioxazine, triarylmethane, xanthene, and anthraquinone. A colored layer of each color can be formed by photolithography using a coloring composition containing these coloring agents and a resin or a polymerizable compound.

Such other colorants include pigments and dyes, and one or more of these other colorants can be contained. When other colorants are contained, the pigment is preferably an organic pigment, and the dye is preferably an organic dye, from the viewpoint of obtaining pixels with high brightness, contrast and coloring strength.

The organic dye is not particularly limited, and for example, compounds classified as Dye in the Color Index (published by CI: The Society of Dyers and Colorists) and other known dyes are used. be able to. Examples of such dyes include triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, azo dyes, dipyrromethene dyes, quinophthalone dyes, coumarin dyes, pyrazolone dyes, quinoline dyes, nitro Dyes, quinone imine dyes, phthalocyanine dyes, squarylium dyes and the like can be mentioned. Among them, triarylmethane dyes, cyanine dyes, xanthene dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable from the viewpoint of heat resistance.

Examples of organic pigments include compounds classified as pigments in the Color Index (CI: published by The Society of Dyers and Colourists). .) Numbered ones can be preferably used.

C. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I. I. Pigment Red 269, C.I. I. a red pigment such as Pigment Red 279;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Green pigments such as Pigment Green 63;
C. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 79, C.I. I. a blue pigment such as Pigment Blue 80;
C. I. Pigment Yellow 83, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 179, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 211, C.I. I. Pigment Yellow 215, C.I. I. a yellow pigment such as Pigment Yellow 231;
C. I. an orange pigment such as Pigment Orange 38;
C. I. Pigment Violet 19, C.I. I. purple pigments such as Pigment Violet 23;

In addition, a brominated diketopyrrolopyrrole pigment represented by formula (Ic) in JP-T-2011-523433 can also be used as a red pigment. In addition, JP 2001-081348, JP 2010-026334, JP 2010-191304, JP 2010-237384, JP 2010-237569, JP 2011-006602, Lake pigments described in JP-A-2011-145346 can be mentioned.

In one embodiment of the present invention, when a pigment is contained as a colorant, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof before use. can. Moreover, if desired, the pigment may be used after modifying its particle surface with a resin. Examples of resins for modifying the surface of pigment particles include vehicle resins described in JP-A-2001-108817 and various commercially available resins for dispersing pigments. As a method for coating the carbon black surface with a resin, for example, the methods described in JP-A-9-71733, JP-A-9-95625, and JP-A-9-124969 can be employed. Further, the organic pigment may be used after making the primary particles fine by so-called salt milling. As the salt milling method, for example, the method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

Moreover, in one embodiment of the present invention, when a pigment is contained as a coloring agent, at least one selected from known dispersants and dispersing aids can be further contained.

3-4. Alignment Film A liquid crystal alignment agent containing polyamic acid as a main component can be used as a liquid crystal alignment agent for forming the alignment film used in the liquid crystal display device of the present embodiment.

Furthermore, the liquid crystal aligning agent of this Embodiment can be made into the liquid crystal aligning agent which has a photo-alignment function by containing the polymer which has a photo-alignment group. All of these can form an alignment film at a low heating temperature such as 200° C. or lower. Moreover, other components can be contained as long as they do not impair the effects of the present invention.

The photo-orientation group is a functional group that imparts anisotropy to the film by light irradiation. It is a group that imparts anisotropy to the film.

Specific examples of photoorientable groups include cyclobutane ring, azobenzene, stilbene, α-imino-β-ketoester, spiropyran, spirooxazine, cinnamic acid, chalcone, stilbazole, benzylidenephthalimidine, coumarin, diphenylacetylene and anthracene. It is a group having a structure derived from at least one compound selected from the group consisting of; Among these, groups having a structure derived from cinnamic acid are particularly preferable as the above-described photo-orientable groups.

The polymer having a photo-alignment group is preferably a polymer in which the above-mentioned photo-alignment group is bonded directly or via a linking group. Such polymers include, for example, at least one of polyamic acids, polyamic acid esters, and polyimides, to which the above-described photo-alignable groups are bonded, and polymers other than polyamic acids and polyimides. to which the photo-orientation group is bonded. In the latter case, examples of the basic skeleton of the polymer having photoalignable groups include poly(meth)acrylic acid esters, poly(meth)acrylamides, polyvinyl ethers, polyolefins, and polyorganosiloxanes.

As the radiation-sensitive polymer, those having a basic skeleton of polyamic acid, polyimide or polyorganosiloxane are preferred. Among these, polyorganosiloxane is particularly preferred, and can be obtained, for example, by the method described in International Publication No. 2009/025386.

The polyamic acid contained in the liquid crystal aligning agent becomes a polyimide by dehydration ring closure and imidization. Such a polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine, and can be obtained as described in JP-A-2010-97188.

Polyamic acid ester can be obtained, for example, by a method of reacting a tetracarboxylic acid diester dihalide and a diamine compound, and can be obtained, for example, as described in JP-A-2017-200991.

The polyimide may be a complete imidized product obtained by dehydrating and ring-closing all the amic acid structures of the precursor polyamic acid, and only a part of the amic acid structure is dehydrated and ring-closed to form the amic acid structure and the imide. It may be a partially imidized compound in which a ring structure coexists. The polyimide preferably has an imidization rate of 30% or more, more preferably 50% to 99%, even more preferably 65% to 99%. The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amic acid structures and the number of imide ring structures of the polyimide. Here, a part of the imide ring may be an isoimide ring, which can be obtained, for example, as described in JP-A-2010-97188.

Moreover, the liquid crystal aligning agent in one Embodiment of this invention can contain the crosslinking agent which has a specific crosslinkable group. By including such a cross-linking agent, an alignment film having excellent solvent resistance, heat resistance, rubbing resistance, etc. can be formed even when the alignment film is formed in a process in which the alignment film is formed at a baking temperature of 200° C. or less. be able to. As such a cross-linking agent, compounds containing two or more cross-linkable groups such as (meth)acryloyl groups, vinyl groups, epoxy groups, oxetanyl groups, alkoxysilyl groups, alkoxyl groups and isocyanate groups in one molecule are preferred. Among the above alkoxyl groups, a methoxy group is particularly preferable from the viewpoint of reactivity, and an isocyanate group can also be used as a blocked isocyanate group. As such compounds, add-1 to add-6 compounds shown below are preferable. More preferably, it is contained in the range of 1 to 20 parts by mass. By containing it in such a range, it is possible to form an alignment film having excellent mechanical strength such as solvent resistance, heat resistance and rubbing resistance even in a low-temperature baking process of 200° C. or less.

ａｄｄ－６としては、イソシアネート基もしくはブロックされたイソシアネート基を有する化合物であり、これらの具体例としては、２－メタクリロイルオキシエチルイソシアネート（昭和電工（株）製 カレンズＭＯＩ），メタクリル酸 ２－（Ｏ－［１‘－メチルプロピリデンアミノ］カルボキシアミノ）エチル（昭和電工（株）製 カレンズＭＯＩ―ＢＭ），２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］エチルメタクリレート（昭和電工（株）製 カレンズＭＯＩ―ＢＰ）等を用いることができる。

Add-6 is a compound having an isocyanate group or a blocked isocyanate group. - [1'-methylpropylideneamino] carboxyamino) ethyl (manufactured by Showa Denko K.K. Karenz MOI-BM), 2-[(3,5-dimethylpyrazolyl)carbonylamino] ethyl methacrylate (manufactured by Showa Denko K.K. Karenz MOI-BP) or the like can be used.

Further, the liquid crystal aligning agent according to one embodiment of the present invention is at least one selected from the group consisting of compounds represented by the following formulas (E-1) to (E-5), and one An organic solvent having a boiling point at atmospheric pressure of 180° C. or less can be contained.

By using the above specific solvents (E-1) to (E-5) as at least part of the solvent component of the liquid crystal aligning agent, even when the heating at the time of film formation is performed at a low temperature (for example, 200 ° C. or less) This is preferable in that a liquid crystal element having excellent liquid crystal orientation and electrical properties can be obtained.

In addition, even when a low boiling point solvent such as the above specific solvent is used, the coating properties on the substrate (suppression of film thickness unevenness and pinholes, ensuring linearity and flatness of the edge of the coating area) are excellent, and This is preferable in that a liquid crystal element having good liquid crystal orientation and good electrical properties can be obtained.

（式（Ｅ－１）中、Ｒ^４１は、炭素数１～４のアルキル基又はＣＨ_３ＣＯ－であり、Ｒ⁴²は、炭素数１～４のアルカンジイル基又は－（Ｒ^４７－Ｏ）ｒ－Ｒ^４８－（ただし、Ｒ^４７及びＲ^４８は、それぞれ独立に炭素数２又は３のアルカンジイル基であり、ｒは１～４の整数である。）であり、Ｒ^４３は、水素原子又は炭素数１～４のアルキル基である。）

(In formula (E-1), R ⁴¹ is an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—, and R ⁴² is an alkanediyl group having 1 to 4 carbon atoms or —(R ⁴⁷ —O) r—R ⁴⁸ — (where R ⁴⁷ and R ⁴⁸ are each independently an alkanediyl group having 2 or 3 carbon atoms, and r is an integer of 1 to 4), and R ⁴³ is a hydrogen atom; or an alkyl group having 1 to 4 carbon atoms.)

（式（Ｅ－２）中、Ｒ^４４は、炭素数１～４のアルカンジイル基である。）

(In formula (E-2), R ⁴⁴ is an alkanediyl group having 1 to 4 carbon atoms.)

（式（Ｅ－３）中、Ｒ^４５及びＲ^４６は、それぞれ独立に炭素数１～８のアルキル基である。）

(In formula (E-3), R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 8 carbon atoms.)

（式（Ｅ－４）中、Ｒ^４９は、水素原子又は水酸基であり、Ｒ^５０は、Ｒ^４９が水素原子の場合、炭素数１～９の炭化水素基であり、Ｒ^４９が水酸基の場合、炭素数１～９の２価の炭化水素基又は当該炭素－炭素結合間に酸素原子を有する２価の基である。）

(In formula (E-4), R ⁴⁹ is a hydrogen atom or a hydroxyl group, R ⁵⁰ is a hydrocarbon group having 1 to 9 carbon atoms when R ⁴⁹ is a hydrogen atom, and when R ⁴⁹ is a hydroxyl group , a divalent hydrocarbon group having 1 to 9 carbon atoms or a divalent group having an oxygen atom between the carbon-carbon bonds.)

（式（Ｅ－５）中、Ｒ^５１及びＲ^５２は、それぞれ独立に炭素数１～６の１価の炭化水素基又は当該炭素－炭素結合間に酸素原子を有する１価の基である。）

(In formula (E-5), R ⁵¹ and R ⁵² are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent group having an oxygen atom between the carbon-carbon bonds. )

Specific examples of the specific solvent include compounds represented by formula (E-1) above, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxy-1-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether;
Examples of compounds represented by the above formula (E-2) include cyclobutanone, cyclopentanone, and cyclohexanone;
Examples of compounds represented by the above formula (E-3) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl- n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diisobutyl ketones, etc.;
Examples of compounds represented by the above formula (E-4) include methanol, ethanol, propanol, butanol, pentanol, 3-methoxybutanol, hexanol, heptanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3, Monoalcohols such as 3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol, and polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol and 2,4-pentanediol;
Examples of compounds represented by the above formula (E-5) include partial esters of polyhydric alcohols (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol). Partial esters of polyhydric alcohols such as monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether), Methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, acetic acid Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, Examples include n-butyl propionate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate and the like. In addition, as a specific solvent, you may use individually by 1 type, and may use it in combination of 2 or more types.

The solvent component of the liquid crystal aligning agent may consist of only the specific solvent, or may be a mixed solvent of other solvents other than the specific solvent and the specific solvent. Other solvents include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidinone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, Highly polar solvents such as N,N-dimethylacetamide;
4-hydroxy-4-methyl-2-pentanone, butyl lactate, butyl acetate, methylmethoxypropionate, ethylethoxypropionate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, cyclohexane, octanol, tetrahydrofuran and the like. These can be used individually by 1 type or in mixture of 2 or more types.

Among the above-mentioned other solvents, highly polar solvents can be used for the purpose of further improving solubility and leveling properties. A hydrocarbon-based solvent that does not contain an amide structure can also be used for the purpose of enabling application to plastic substrates and low-temperature firing.

Regarding the solvent component contained in the liquid crystal aligning agent, the content of the specific solvent is preferably 20% by mass or more, and is 40% by mass or more, relative to the total amount of the solvent contained in the liquid crystal aligning agent. is more preferable, more preferably 50% by mass or more, and particularly preferably 80% by mass or more. The liquid crystal aligning agent according to one embodiment of the present invention is suitable in that a liquid crystal element having excellent liquid crystal alignment and electrical properties can be obtained even when the solvent component in the liquid crystal aligning agent is only a specific solvent.

The liquid crystal aligning agent according to one embodiment of the present invention can obtain a liquid crystal element having excellent liquid crystal alignment and electrical properties even when it does not substantially contain N-methyl-2-pyrrolidone (NMP). preferred. In this specification, "substantially does not contain NMP" means that the content of NMP is preferably 5% by mass or less, more preferably 3% by mass, with respect to the total amount of the solvent contained in the liquid crystal aligning agent. % by mass or less, more preferably 0.5% by mass or less.

The solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It is in the range of 1 to 10% by mass. If the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, making it difficult to obtain a good liquid crystal alignment film. On the other hand, if the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes excessively large, making it difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, resulting in poor applicability. There is a tendency.

The liquid crystal aligning agent according to one embodiment of the present invention is prepared as a solution-like composition in which the polymer component and optionally blended components are preferably dissolved in an organic solvent. Examples of the organic solvent include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The solvent component may be one of these, or a mixed solvent of two or more.

Furthermore, the liquid crystal aligning agent according to one embodiment of the present invention includes at least A liquid crystal aligning agent containing a kind of polymer can be used. Styrenic polymers containing aromatic hydrocarbon groups, (meth)acrylic polymers, polysiloxanes, polyamic acids and polyamic acid derivatives can be used alone, or two or more of them can be used in combination. good. When two or more polymers are used in combination, polyamic acid and polyamic acid derivative polyamic acid and styrene polymer, polyamic Acid and Polyamic Acid Derivative Combinations of polyamic acid and polysiloxane, polysiloxane and (meth)acrylic polymer, etc. are preferred.

Liquid crystal aligning agents containing (meth)acrylic polymers and styrene polymers, polysiloxanes, and the like are further combined with a group having at least one of an oxetane ring and an oxirane ring, and an oxetane ring and an oxirane ring by heating. It can use for a liquid crystal aligning agent as a polymer which has a functional group which reacts with at least any.

At least one of the oxetane ring and the oxirane ring reacts with other functional groups such as a carboxyl group by heating to open the ring and form a crosslinked structure. In this cross-linking reaction, another functional group such as a carboxyl group and at least one ring structure of an oxetane ring and an oxirane ring form a cross-linked structure by heating within the same molecular chain or between other molecular chains. By forming such a crosslinked structure in the alignment film, an alignment film having excellent heat resistance and the like can be formed.

Liquid crystal alignment agents containing such (meth)acrylic polymers and styrene polymers include International Publication No. 2017/115791, International Application No. PCT/JP2017/037832, and International Application No. PCT/JP2017/037833. The liquid crystal aligning agent described in is preferable.

3-5. Protective Film The curable composition used for forming the protective film contains a polymer and a polymerizable compound, and if necessary, may contain an acid generator, a polymerization initiator, and the like. Furthermore, surfactants and adhesion aids can be included as optional components. As such a curable composition, a curable composition described in JP-A-2013-24928 or the like can be used.

The coating film formed from the curable composition can be cured by heat or by exposure to light. It is also possible to easily form a fine and elaborate pattern by exposure and development utilizing radiation sensitivity, and achieves low-temperature curing. Such a protective film is formed on the color filter, can realize a highly flat film on the color filter, and can achieve high film thickness uniformity in spacer formation, alignment film formation, and transparent electrode formation.

3-6. Spacers Spacers are used to form the cell gap of the liquid crystal layer between the glass substrates. The spacer-forming curable composition contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator, and may further contain optional components. The curable composition can easily form a fine and elaborate pattern by exposure and development utilizing its radiation sensitivity, and achieves low-temperature curing.

As the alkali-soluble resin, an alkali-soluble resin that is a copolymer containing a structural unit formed from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a structural unit formed from an unsaturated compound containing an epoxy group is used. be able to. As such a curable composition, a curable composition described in JP-A-2012-242442 can be used.

Spacers can be formed by low temperature curing by using a specific curing accelerator. Specifically, a spacer having good reliability can be obtained at a curing temperature of 200° C. or less, and even at a curing temperature of 180° C. or less.

3-7. Interlayer insulating film A radiation-sensitive resin composition is used for forming an interlayer insulating film, and the radiation-sensitive resin composition contains an alkali-soluble resin and a photosensitive agent. In addition to excellent film transparency and heat resistance, the film must have patterning properties for forming contact holes. From this point of view, the resin contained in the radiation-sensitive resin composition of the present embodiment is preferably at least one selected from acrylic resins having carboxyl groups, polyimide resins, polysiloxanes and novolak resins. Each of these resins can be used alone, or can be used in combination. A chemically amplified resin having a protective group can also be used as the acrylic resin.

There are no particular restrictions on the use of a mixture of resins, but in that case, it is particularly preferable to use the novolac resin by mixing it with other resins from the above-described viewpoint. Further, it is preferable to use a mixture of a novolak resin and an acrylic resin having a carboxyl group, and to use a mixture of a novolak resin and a polyimide resin.

A quinonediazide compound and a photoacid generator compound can be used as the photosensitizer. As the radiation-sensitive resin composition for forming such an interlayer insulating film, the compositions described in JP-A-2013-219173, JP-A-2013-105136, and JP-A-2014-39010 can be used. can.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight Mw, number average molecular weight Mn and epoxy equivalent of the polymer, and the solution viscosity of the polymer solution were measured by the following methods. Necessary amounts of the raw material compounds and polymers used in the following examples were ensured by repeating the synthesis on the synthesis scale shown in the synthesis examples below as necessary.

1-1. Weight average molecular weight Mw and number average molecular weight Mn of the polymer
Mw and Mn are polystyrene conversion values measured by GPC under the following conditions.
Column: TSKgelGRCXLII manufactured by Tosoh Corporation
Solvent: Tetrahydrofuran, or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40°C
Pressure: 68kgf/ ^cm2

1-2. Epoxy Equivalent Epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2015.

1-3. Solution Viscosity of Polymer Solution The solution viscosity (mPa·s) of the polymer solution was measured at 25° C. using an E-type rotational viscometer.

2. Polymer Synthesis Examples Synthesis examples of polymers are shown below.

2-1. Synthesis Example 1-1
Under nitrogen, in a 100 mL two-necked flask, as polymerization monomers, compound (MI-1) 5.00 g (8.6 mmol), 4-vinylbenzoic acid (M-2) 0.64 g (4.3 mmol), 4-( 2,5-dioxo-3-pyrrolin-1-yl)benzoic acid (M-3) 2.82g (13.0mmol) and 4-(glycidyloxymethyl)styrene (M-1) 3.29g (17. 2 mmol), 2,2′-azobis(2,4-dimethylvaleronitrile) 0.31 g (1.3 mmol) as a radical polymerization initiator, and 2,4-diphenyl-4-methyl-1-pentene 0 as a chain transfer agent. 0.52 g (2.2 mmol) and 25 ml of tetrahydrofuran as a solvent were added and polymerized at 70° C. for 5 hours. After reprecipitation in n-hexane, the precipitate was filtered and vacuum-dried at room temperature for 8 hours to obtain the desired polymer (P-1). The weight average molecular weight Mw measured in terms of polystyrene by GPC was 30,000, and the molecular weight distribution Mw/Mn was 2.

2-2. Synthesis Example 1-2
Polymerization was carried out in the same manner except that the types and molar ratios of the polymerization monomers were as shown in Table 1 below, and the compound (MI-1) in Synthesis Example 1-1 was changed to the compound (MI-2) to obtain the polymer (P- A polymer (P-2) having the same weight average molecular weight and molecular weight distribution as those of 1) was obtained. The total number of moles of polymerized monomers was 43.1 mmol as in Synthesis Example 1-1 above. The numerical values in Table 1 represent the charged amount (mol%) of each monomer with respect to all the monomers used in polymer synthesis.

The monomer components used in the above synthesis examples are shown below.

Table 1 shows the charged amounts (mol parts) of each monomer with respect to all the monomers used in synthesizing the polymers of Synthesis Examples 1-1 and 1-2.

2-3. Synthesis Example 2-1
13.8 g (70.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 16.3 g of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine (76.9 mmol) was dissolved in 170 g of NMP and reacted at 25° C. for 3 hours to obtain a solution containing 10% by mass of polyamic acid. This polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40° C. under reduced pressure for 15 hours to obtain polyamic acid (PAA-1).

2-4. Synthesis Example 2-2
Polymerization was carried out in the same manner as in Synthesis Example 2-1 except that the types and molar ratios of the polymerization monomers were as shown in Table 2 below to obtain a polymer (PAA-2). In Table 2, the numerical values in the acid dianhydride column indicate the ratio (mol parts) of each compound used with respect to the total amount of 100 mol parts of the tetracarboxylic dianhydride used in the polymerization, and the numerical values in the diamine column. indicates the usage ratio (mol parts) of each compound with respect to the total 100 mol parts of diamines used in the polymerization.

In Table 2, AN-1 is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, AN-2 is 2,3,5-tricarboxycyclopentylacetic dianhydride, and DA-1 is , 2,2′-dimethyl-4,4′-diaminobiphenyl, DA-2 is cholestanyloxy-2,4-diaminobenzene, DA-4 is 4,4′-diaminodiphenylmethane, DA -3 is a chemical substance represented by the following structural formula.

Table 2 shows the charged amounts (mol parts) of each monomer with respect to all the monomers used in synthesizing the polymers of Synthesis Examples 2-1 and 2-2.

3. Synthesis Examples of Polysiloxanes Having Epoxy Groups Synthesis examples of polysiloxanes having epoxy groups are shown below.

3-1. Synthesis example 3
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine are added. Charged and mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was allowed to proceed at 80° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous solution of ammonium nitrate until the water after washing became neutral. (This will be referred to as "polysiloxane (SEp-1)") was obtained as a viscous transparent liquid. When polysiloxane (SEp-1) was subjected to ¹ H-NMR analysis, a peak based on the epoxy group was obtained near the chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. was confirmed. The polysiloxane (SEp-1) had a weight average molecular weight (Mw) of 2,200 and an epoxy equivalent of 186 g/mol.

4. Synthesis Examples of Polysiloxane Having Photo-Orientation Groups Synthesis examples of polysiloxane having photo-orientation groups are shown below.

4-1. Synthesis Example 4-1
In a 200 mL three-necked flask, 11.6 g of the polysiloxane (SEp-1) obtained in Synthesis Example 3, 80 g of methyl isobutyl ketone, 4.0 g of cinnamic acid derivative (C-1) (epoxy contained in polysiloxane (SEp-1) 4.8 g of cinnamic acid derivative (C-1) (corresponding to 15 mol% of epoxy groups possessed by polysiloxane (EPS-1)), and UCAT 0.10 g of 18X (trade name, curing agent for epoxy compounds manufactured by San-Apro Co., Ltd.) was charged and reacted at 100° C. for 48 hours with stirring. After completion of the reaction, methanol was added to the reaction mixture to generate a precipitate. A solution obtained by dissolving the obtained precipitate in ethyl acetate was washed with water three times, the organic layer was dried over magnesium sulfate, and the solvent was distilled off to obtain a white polysiloxane (POS-1). 18.3 g of powder were obtained. The weight average molecular weight Mw of polysiloxane (POS-1) was 5,000.

4-2. Synthesis Example 4-2
The same operation as in Synthesis Example 4-1 was performed except that the type of carboxylic acid used in the reaction was changed to (C-2) or (C-3) and the amount used was changed as shown in Table 3 below, A polymer (POS-2), which is a photo-alignable polyorganosiloxane, was obtained. The numbers in the table represent the ratio (parts by mole) of the carboxylic acid to 100 parts by moles of the epoxy groups contained in the epoxy group-containing polyorganosiloxane used.

The monomers (C-1) to (C-3) used in the above synthesis examples are shown below.

Table 3 shows the charged amounts (moles) of the carboxylic acid monomers used in synthesizing the polysiloxanes of Synthesis Examples 4-1 and 4-2.

1. Preparation of Liquid Crystal Aligning Agent As polymer components, the polymer (P-1) obtained in Synthesis Example 1-1 was added with propylene glycol monomethyl ether (PGME), MB (3-methoxy-1-butanol) and diacetone as solvents. Alcohol (DAA) was added to prepare a solid content concentration of 4% by mass and a mass ratio of each solvent to be PGME:MB:DAA=50:40:10. Next, the resulting polymer solution was filtered through a filter with a pore size of 0.2 μm to prepare a liquid crystal aligning agent (AL-1).

Further, liquid crystal aligning agents (AL-2) to (A-6) were prepared in the same manner as in the preparation of liquid crystal aligning agent (AL-1), except that each component of the type and compounding amount shown in Table 4 below was used. were prepared respectively.

In Table 4, PGME is propylene glycol monomethyl ether, CPN is cyclopentanone, MB is 3-methoxy-1-butanol, DAA is diacetone alcohol, BC is butyl cellosolve, EDM is diethylene glycol ethyl methyl ether, and DEDG is diethylene glycol diethyl. Ether, NMP denotes N-methyl-2-pyrrolidone.

2. Interlayer insulating film Synthesis examples of the polymer used for the radiation-sensitive resin composition for forming the interlayer insulating film are shown below.

2-1. Synthesis Example 1 (synthesis of resin (α-I))
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, 10 parts by weight of styrene, 12 parts by weight of tetrahydrofurfuryl methacrylate, 15 parts by weight of N-cyclohexylmaleimide and n- After charging 10 parts by mass of lauryl methacrylate and purging with nitrogen, the temperature of the solution is raised to 70° C. while gently stirring, and this temperature is maintained for 5 hours for polymerization to obtain a resin (α- A solution containing I) was obtained. Mw of resin (α-I), which is a copolymer, was 8,000.

2-2. Synthesis Example 2 (synthesis of resin (α-II))
Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Central Glass Co., Ltd.) 29.30 g (0.08 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane 1 under dry nitrogen stream .24 g (0.005 mol), 3-aminophenol (Tokyo Chemical Industry Co., Ltd.) 3.27 g (0.03 mol) as a terminal blocking agent, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 80 g was dissolved. 31.2 g (0.1 mol) of bis(3,4-dicarboxyphenyl) ether dianhydride (Manac Co., Ltd.) was added together with 20 g of NMP, reacted at 20° C. for 1 hour, and then reacted at 50° C. for 4 hours. let me After that, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while azeotroping water with the xylene. After stirring, the solution was put into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80° C. for 20 hours to obtain resin (α-II) as a polymer having a structure represented by the following formula (3). rice field.

2-3. Synthesis Example 3 (synthesis of resin (α-III))
Into a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane, and heated until the solution temperature reached 60°C. . After the solution temperature reached 60° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75° C., and held for 4 hours. Further, the temperature of the solution was set to 40° C., and evaporation was carried out while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolytic condensation. As described above, a resin (α-III) was obtained as a siloxane polymer, which is a hydrolytic condensate. Mw of Resin (α-III), which is a siloxane polymer, was 5,000.

2-4. Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by mass of methacrylic acid, 40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of α-methylstyrene dimer were charged and nitrogen-substituted. After that, gentle stirring was started. The temperature of the solution was raised to 70° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing polymer (α-IV). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-1) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.1% by mass.

A preparation example of a radiation-sensitive resin composition for forming an interlayer insulating film is shown.

A solution containing the resin (α-I) of Synthesis Example 1 was added in an amount corresponding to 100 parts by mass (solid content) of the copolymer and 4,4′-[1-{4-(1-[ 30 parts by mass of 4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol (1.0 mol) and 2 parts by mass of benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate as a thermal acid generator are mixed, After dissolving it in diethylene glycol ethyl methyl ether, it was filtered through a membrane filter with a diameter of 0.2 μm to prepare a radiation-sensitive resin composition (J-1) for forming an interlayer insulating film.

2 g of a novolak resin (trade name, XPS-4958G, m-cresol/p-cresol ratio = 55/45 (weight ratio), Gunei Chemical Industry Co., Ltd.) was added to 8 g of the resin (α-II) of Synthesis Example 2. . Furthermore, 2.4 g of a compound represented by the following formula (β1) and 0.6 g of a compound represented by the following formula (β2) were added as thermal cross-linkable compounds that undergo a cross-linking reaction by heat, and 2 g of a quinonediazide compound (β3) was added. , and γ-butyrolactone as a solvent was added to these and dissolved, and filtered through a membrane filter with a diameter of 0.2 μm to prepare a radiation-sensitive resin composition for forming an interlayer insulating film (J-2).

A preparation example of the radiation-sensitive resin composition (β-III) is shown.

4,4'-[1-{ Condensation of 4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol (1.0 mol) with 1,2-naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol) and 0.1 part by mass of a fluorosurfactant (FTX-218, manufactured by Neos) as a surfactant, and propylene glycol monomethyl ether was added so that the solid content concentration was 25% by mass. A radiation-sensitive resin composition (J-3) for forming an interlayer insulating film was prepared.

A solution containing the polymer (α-IV) obtained in Synthesis Example 4, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile (Ciba Specialty Chemicals, IRGACURE PAG 103) 3 parts by mass, [C] diethylene glycol ethyl methyl ether as an organic solvent, [D] silicone surfactant as a surfactant (Toray Dow Corning, SH 8400 FLUID ) and filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (J-4) for forming an interlayer insulating film.

Synthesis examples of the polymer used for the curable composition for forming a flattening film are shown.

A flask equipped with a condenser and stirrer was charged with 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo[5.2.1.02,6]decan-8-yl methacrylate, 38 parts by mass of methyl methacrylate, 10 parts by mass of styrene, and 20 parts by mass of glycidyl methacrylate were charged, and nitrogen was added. After the replacement, the temperature of the solution was raised to 70° C. while gently stirring, and polymerization was performed while maintaining this temperature for 4 hours to obtain a solution containing the copolymer (A-1) (solid concentration = 34.4% by mass, Mw = 8,000, Mw/Mn = 2.3). The solid content concentration means the ratio of the copolymer mass to the total mass of the copolymer solution.

A preparation example of a curable resin composition for forming a flattening film is shown.

With respect to 100 parts by mass of the copolymer (A-1) obtained in Example 7, 100 parts by mass of dipentaerythritol hexaacrylate (B-1) as a [B] polymerizable compound, [C] as a polymerization initiator 1.2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF) (C-1) 5 parts by mass, and [D] as a compound 4,4'-Diaminodiphenylsulfone (D-1) is mixed, and further [J-1] 5 parts by mass of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, [J-2] Surfactant (FTX -218, Neos) 0.5 parts by mass, [J-3] 0.5 parts by mass of 4-methoxyphenol as a storage stabilizer, and propylene glycol monomethyl, respectively, so that the solid content concentration is 30% by mass A radiation-sensitive resin composition (K-1) was prepared by adding ether acetate and filtering through a Millipore filter with a pore size of 0.5 μm.

A synthesis example of the compound [A] as a polymer used in the radiation-sensitive resin composition for forming a photospacer is shown below.

A flask equipped with a condenser and stirrer was charged with 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo[5.2.1.02,6]decan-8-yl methacrylate, 38 parts by mass of methyl methacrylate, 10 parts by mass of styrene, and 20 parts by mass of glycidyl methacrylate were charged, and nitrogen was added. After the substitution, the temperature of the solution was raised to 70° C. while gently stirring, and this temperature was maintained for 4 hours for polymerization to obtain a copolymer (A- A solution containing 1) was obtained (solid concentration = 34.4% by mass, Mw = 8,000, Mw/Mn = 2.3). The solid content concentration means the ratio of the copolymer mass to the total mass of the copolymer solution.

A preparation example of a radiation-sensitive resin composition for forming a photospacer is shown.

With respect to 100 parts by mass of the copolymer (A-1) obtained in Example 6, 100 parts by mass of dipentaerythritol hexaacrylate (B-1) as a [B] polymerizable compound, [C] as a polymerization initiator Ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE02, manufactured by BASF) (C-1) is added to 5 4,4'-diaminodiphenylsulfone (D-1) as a [D] compound, and 5 parts by mass of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, a surfactant (FTX- 218, Neos Co.) 0.5 parts by mass and 0.5 parts by mass of 4-methoxyphenol as a storage stabilizer are mixed, and propylene glycol monomethyl ether acetate is added so that the solid content concentration becomes 30% by mass. A radiation-sensitive resin composition (L-1) was prepared by filtering through a Millipore filter having a pore size of 0.5 μm.

1. Synthesis example of polymer used for colored pattern forming resin composition 1-1. [I] Synthesis of alkali-soluble resin (B-1) A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, and 2-ethylhexyl methacrylate. 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl) succinate and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) It was added dropwise over time and polymerized for 2 hours while maintaining this temperature. After that, the temperature of the reaction solution was raised to 100° C., and polymerization was further performed for 1 hour to obtain a binder resin solution (solid concentration: 33% by mass). The resulting binder resin had an Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "binder resin (B-1)".

2. Preparation of colorant dispersion (MB-R-1) 2-1. Preparation example 1
(A) C.I. I. 10.1 parts by weight of Pigment Red 177, 2.9 parts by weight of Pigment Yellow 139, BYK-LPN21116 as a dispersant (manufactured by BYK-Chemie, solid content concentration 40.0% by weight) in a solution of 12.5 parts by weight, binder A mixture of 15.2 parts by mass of a solution of polymer (B-1) (solid concentration: 33% by mass) and 53.4 parts by mass of propylene glycol methyl ether acetate and 5.9 parts by mass of propylene glycol monomethyl ether as solvents was prepared. , and mixed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (MB-R-1).

2-2. Colorant dispersions (MB-R-2) to (MB-R-8), (MB-G-1) to (MB-G-8), (MB-R-2) to (MB-R-8) )
In Preparation Example 1, a colorant dispersion (MB- R-2) ~ (MB-R-8), (MB-G-1) ~ (MB-G-8), (MB-R-2) ~ (MB-R-8) were prepared. Table 5 shows the colorants of the above colored dispersions and their chromaticity results.

In Table 5, BL-1, BL-2, and BL-3 each indicate a white light source of the backlight, and BL-1 is BLUE-LED (λmax = 455 nm) / GREEN-LED (λmax = 523 nm) / KSF fluorescence BL-2 represents BLUE-LED (λmax=445 nm)/βSiAlON phosphor/KSF phosphor, and BL-3 represents BLUE-LED/YAG. In Table 5, V-dye indicates a dye having the following structure.

1. Preparation of colored pattern-forming resin composition 100 parts by mass of colorant dispersion (MB-R-1), (B) 13.8 parts by mass of solution of binder polymer (B-1) as alkali-soluble resin, (D) As the polymerizable compound, (D-1) a monoester compound of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol hexaacrylate and 7 parts by mass of a mixture of dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd., trade name Aronix M-520), (E) as a photopolymerization initiator, (E-1) 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (manufactured by BASF, commercial name IRGACURE369) 0.7 parts by mass, (E-2) oxime initiator (manufactured by ADEKA, trade name NCI-831) 0.8 parts by mass, fluorosurfactant Megafac F-554 (DIC Corporation 0.03 parts by mass of the product), add methoxybutyl acetate in an amount corresponding to 10% of the total solvent amount so that the solid content concentration becomes 17.0%, and further add an amount corresponding to the remaining solvent amount. Propylene glycol monomethyl ether acetate was added to prepare a coloring composition (R-1).

Table 6 from red coloring composition (R-2) to (R-10), green coloring composition (G-1) to (G-11), blue coloring composition (B-1) to (B -10). Also, as comparative examples, Table 6 shows red coloring compositions (r-1) to (r-3), green coloring compositions (g-1) to (g-3), blue coloring compositions (b- 1) to (b-3) are shown.

In Table 6, A-3-1 represents Solvent Blue 70, A-3-2 represents Varifact Orange 3209 (manufactured by Orient Chemical Industry Co., Ltd.), and D-1 represents dipentaerythritol pentaacrylate and succinic acid. monoester compounds, dipentaerythritol hexaacrylate and mixtures with dipentaerythritol pentaacrylate, E-1 is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1- On (manufactured by BASF, trade name IRGACURE369), E-2 indicates ADEKA oxime ester initiator NCI-831, F-1 indicates Megafac F-554 (manufactured by DIC Corporation). , Q-1 indicates Solvent Blue 70, MBA indicates methoxybutyl acetate, and MB indicates 3-methoxybutanol. "-" in the table indicates that it was not added.

The colored composition was evaluated according to the procedure shown in Example 14.

FIG. 7A shows the step of forming a switching element 168. A gate electrode 178, a gate insulating film 176, a semiconductor film 174, a source electrode 179a and a drain electrode 179b are formed on a substrate. As the semiconductor film 174, for example, an oxide semiconductor film containing indium, gallium, and zinc as components having characteristics equivalent to those disclosed in Japanese Patent Application Laid-Open No. 2007-115902 was formed. The gate electrode 178 and the semiconductor film 174 were formed into a predetermined shape by forming a resist mask by photolithography and patterning by etching.

FIG. 7B shows the step of forming an interlayer insulating film, using a radiation-sensitive resin composition (J-1) exemplified in Example 3 on a substrate on which a source electrode 179a and a drain electrode 179b are formed, An organic interlayer insulating film 180 was formed. An ITO film was formed on the organic interlayer insulating film 180 by sputtering and patterned to form a common electrode 171 having a predetermined slit pattern. Furthermore, an insulating film 182 was formed on the common electrode 171 using the radiation-sensitive resin composition (J-1) exemplified in Example 3.

Next, as shown in FIG. 8A, a contact hole was formed through the organic interlayer insulating film 180 and the insulating film 182 to expose the upper surface of the drain electrode 179b, and the pixel electrode 170 was formed. The pixel electrode 170 was formed by sputtering an ITO film, patterning it, and forming a shape having a slit pattern that exposes the common electrode 171 in plan view.

As shown in FIG. 8B, a photospacer 128 was formed on the pixel electrode 170 using the radiation-sensitive resin composition for photospacer formation exemplified in Examples 9 and 10. As shown in FIG. The photospacer 128 was formed at a position overlapping the contact hole of the pixel electrode 170 .

Next, a photo-alignment film was formed on the upper surface of the array substrate 114 on which the pixel electrodes 170 were formed, using a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-alignment group. As a method for forming a photo-alignment film, a liquid crystal aligning agent A-1 described in Example 6 of WO 2009/025386 is used as a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-aligning group with a spinner. Each substrate was coated with the composition, prebaked on a hot plate at 80° C. for 1 minute, and then heated at 180° C. for 1 hour in an oven whose interior was replaced with nitrogen to form a coating film having a thickness of 80 nm. Next, the surface of the coating film was irradiated with 200 J/m ² of polarized ultraviolet light containing an emission line of 313 nm using a Hg-Xe lamp and a Glan-Taylor prism from a direction inclined at 40° with respect to the direction perpendicular to the substrate surface, An alignment film 188a is formed.

As shown in FIG. 9A, a color filter 122 having a light shielding layer 126 and a colored layer 124 was formed on the opposing substrate 116 . The light shielding layer 126 was formed by applying a light shielding material using an inkjet method. The colored layer 124 was formed using a coloring material corresponding to each color shown in the embodiment.

Furthermore, as shown in FIG. 9B, a protective film 186 was formed on the upper surfaces of the light shielding layer 126 and the colored layer 124 . The protective film 186 was formed using the curable resin composition for forming a flattening film described in Example 8.

As shown in FIG. 9C, an alignment film 188b is formed on the protective film 186 in the same manner as in the array substrate 114. As shown in FIG.

After that, a seal pattern (not shown) was formed on the counter substrate 116 so as to surround the region where the pixels were formed. The seal pattern was formed by screen printing an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 3.5 μm.

Then, a negative type liquid crystal (MLC-6608 manufactured by Merck Co., Ltd.) was dropped inside the seal pattern of the opposing substrate 116 . Then, as shown in FIG. 10, an array substrate 114 was attached. After that, in order to remove the flow alignment of the liquid crystal, it was heated at 130° C. and then slowly cooled to room temperature. The array substrate 114 and the counter substrate 116 were bonded together with a certain gap by a photospacer 128, and a liquid crystal layer 118 was formed in the gap.

1. Evaluation of BT2020 coverage rate The coloring composition (R-1) was applied to a soda glass substrate on which a SiO ₂ film was formed to prevent the elution of sodium ions on the surface, using a spin coater, and then hot at 90 ° C. The plate was prebaked for 100 seconds to form a coating film. The rotation speed of the spin coater was adjusted so that the film thickness was 2.6 μm after post-baking.

Then, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm and 436 nm using a high-pressure mercury lamp through a photomask (slit width 90 μm) at an exposure dose of 400 J/m ² . exposed with After that, a developer consisting of a 0.04% by mass aqueous solution of potassium hydroxide at 23° C. was applied to the substrate under the conditions of a developing pressure of 110 kPa and a developer flow rate of 1.2 liters/minute to remove the unexposed film. Shower development was carried out by discharging the developer for a time corresponding to 1.5 times the time until the substrate surface was visible. After that, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230° C. for 20 minutes to form a sample having a red striped colored pattern arranged on the substrate. .

For the prepared sample, the spectrum was measured using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), and the light source BL-1 (BLUE-LED (λmax = 455 nm) / GREEN-LED (λmax = 455 nm) / KSF fluorescence ), the chromaticity (Rx, Ry) in the CIE color system was calculated. Similarly, samples of the coloring composition (G-1) and the coloring composition (B-1) were prepared, and the chromaticities (Gx, Gy) and (Bx, By) were measured. From the chromaticity of each color obtained, the BT2020 color gamut (Rx = 0.708, Ry = 0.292, Gx = 0.170, Gy = 0.797, Bx = 0 .131, By=0.046), the coverage rate ([area of overlapping portion between the area surrounded by the RGB color coordinates and the BT2020 color gamut]/[area of the BT2020 color gamut]×100) was calculated. With respect to the obtained coverage ratio, 85% or more was evaluated as "○", 80% or more as "Δ", and less than 80% as "X".

The coloring composition (R-1) was applied using a spin coater onto a soda glass substrate having a SiO2 film formed on the surface to prevent the elution of sodium ions, and then prebaked on a hot plate at 90°C for 100 seconds. to form a coating film. The rotation speed of the spin coater was adjusted so that the film thickness was 2.6 μm after post-baking.

After cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm and 436 nm at a dose of 400 J/m ² through a photomask (slit width 90 μm) using a high-pressure mercury lamp. exposed with After that, a developer consisting of a 0.04% by mass aqueous solution of potassium hydroxide at 23° C. was applied to the substrate under the conditions of a developing pressure of 110 kPa and a developer flow rate of 1.2 liters/minute to remove the unexposed film. Shower development was carried out by discharging the developer for a time corresponding to 1.5 times the time until the substrate surface was visible. Thereafter, the substrate was washed with ultrapure water, air-dried, and post-baked in a clean oven at 230° C. for 20 minutes to form a red stripe pixel pattern on the substrate. Next, similarly, using the coloring composition (G-1), a green striped pixel pattern is created so as not to overlap the red pixel pattern, and further using the coloring composition (B-1), A blue stripe pixel pattern was produced so as not to overlap the red and green pixel patterns.

2. Evaluation of Development Residue of Coloring Composition Coloring composition (R-1) was coated on a soda glass substrate having a SiO ₂ film formed on the surface to prevent elution of sodium ions using a spin coater, and then the temperature was 90° C. A hot plate was used for 100 seconds to pre-bake to form a coating film of the coloring composition. The rotation speed of the spin coater was adjusted so that the film thickness was 2.6 μm after post-baking.

Then, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm and 436 nm using a high-pressure mercury lamp through a photomask (slit width 90 μm) at an exposure dose of 400 J/m ² . exposed with

After that, a developer consisting of a 0.04% by mass aqueous solution of potassium hydroxide at 23° C. was applied to the substrate under the conditions of a developing pressure of 110 kPa and a developer flow rate of 1.2 liters/minute to remove the unexposed film. Shower development was carried out by discharging the developer for a time corresponding to 1.5 times the time until the substrate surface was visible. After that, the substrate was washed with ultrapure water and air-dried, and then observed with an electron microscope. The development residue was evaluated according to the following evaluation criteria.

A case where no residue was detected on the substrate was rated as "◯", a case where a residue was partially confirmed was rated as "Δ", and a case where a residue was confirmed as a whole was rated as "x". Evaluation results are shown in Tables 7-1, 7-2, and 7-3. Tables 7-1, 7-2, and 7-3 show the contents and evaluation results of each sample of Examples A to Q and Comparative Examples a to f.

3. Sensory test on eye fatigue (evaluation of asthenopia)
20 subjects each with iris colors of brown (dark brown), hazel (light brown), amber (amber), green (green), gray (gray) and blue (blue), for a total of 120 subjects, The TFT of the liquid crystal display element manufactured above was driven, and the following evaluation was performed before and after lighting for 1000 hours. Driving the liquid crystal display element by TFT switches the display in the order of red, green, blue, black, and white every second, and then displays an image of vertical stripes of red, green, and blue for one second. After the display was switched every second in the order of red, green, blue, black, and white, a vertically striped image of red, green, and blue was visually recognized for one second. This was repeated, and a sensory test was conducted after the subjects watched the image for 30 minutes. If the number of people who answered that they did not feel fatigue was 110 or more, "○", if it was 80 or more, it was "△", if it was 70 or more, it was "△△", and if it was less than 70 was evaluated as "x". Table 7-3 shows the evaluation results before and after lighting for 1000 hours.

The liquid crystal display element can reduce eye strain stress, and can be viewed continuously without fatigue. This means that the liquid crystal display element has a color close to the actual color.

4. Evaluation of Visibility of Irregularity The TFTs of the liquid crystal display elements manufactured above were driven on 120 subjects with different iris colors who underwent the above sensory test on eye fatigue, before lighting for 1000 hours and after lighting for 1000 hours. made the following evaluations. In the driving by TFT, the display of the liquid crystal display element was switched in order of red, green, and blue every 20 seconds, and then red, green, and blue were again visually recognized for 20 seconds. When a sensory test was conducted to see if the unevenness was visible, 111 out of 120 people could not visually recognize the unevenness, which was a satisfactory level. If the number of people who answered that they did not feel fatigue was 110 or more, "○", if it was 80 or more, it was "△", if it was 70 or more, it was "△△", and if it was less than 70 was evaluated as "x". Table 7-3 shows the evaluation results before and after lighting for 1000 hours.

In Tables 7-1, 7-2, and 7-3, the liquid crystal panel produced by combining the array substrate produced according to Example 13 and the opposing substrate on which the color filter is formed is referred to as "CF substrate". Examples A to C, J, O, Q and Comparative Examples a, d, f are applicable. In addition, in Tables 7-1, 7-2, and 7-3, a color filter is formed on the array substrate side, an interlayer insulating film is formed thereon, and the same alignment agent and coloring composition as those of the CF substrate are applied. , a composition part for forming an interlayer insulating film, and a composition for forming a photospacer, a liquid crystal panel manufactured by the manufacturing method disclosed in Japanese Patent Application Laid-Open No. 2012-242522 is referred to as a “COA substrate”, and Examples D to I , K to N, P, and Comparative Examples b, c, and e.

As shown in Tables 7-1, 7-2, and 7-3, in Examples AQ, a white light source including a blue LED light source and a red phosphor and a green phosphor, or a blue LED light source and a green LED A high level of coverage of BT2020 can be achieved by combining a white light source, which is a white light source containing a light source and a red phosphor, with a color filter that can reliably cover a specific chromaticity point, and manufacturing of color filters In addition, it was possible to obtain a panel with an effect of suppressing eye strain in the panel evaluation and with good visibility of unevenness.

On the other hand, in Comparative Examples a to f, it was difficult to achieve a high level of both the coverage of BT2020, the residual of the coloring composition, the effect of suppressing eyestrain, and the visibility of unevenness.
rice field.

From these results, it was found that by using an alignment agent that can be fired at a low temperature of 200° C. or less to prepare a color filter using a coloring composition containing a specific coloring agent, a protective film, a spacer forming material, or an interlayer insulating film forming material, It was found that the coverage ratio of BT2020, the residual of the coloring composition, the effect of suppressing eyestrain, and the visibility of unevenness can all be achieved at a high level.

DESCRIPTION OF SYMBOLS 100... Liquid crystal display device, 102... Display panel, 104... Backlight, 106... White light source, 108... Light-guide plate, 109... Reflective member, 110... Optical film, DESCRIPTION OF SYMBOLS 112... Polarizing plate, 114... Array substrate, 116... Counter substrate, 118... Liquid crystal layer, 120... Circuit element layer, 122... Color filter, 124... Colored layer, 126... Light shielding layer 128... Spacer 130... Sealant 132... Front frame 134... Casing frame 136... Diffusion sheet 138... Prism sheet 140. Diffusion plate 142 Reflective polarizing sheet 144 Heat dissipation member 146 Chassis 148 Monochromatic light source 150 Wavelength conversion layer 152 Red phosphor 154... Green phosphor, 156... Bottom plate, 158... Package, 160... Lead frame, 162... Cover glass, 164... Pixel part, 166... Pixel, 168... switching element 170 pixel electrode 171 common electrode 172 underlying insulating film 174 semiconductor film 176 gate insulating film 178 gate electrode 179. Electrode 180 Organic interlayer insulating film 182 Insulating film 184 Insulating film 186 Protective film 188 Alignment film

Claims (19)

A first white light source containing a blue light source, a red phosphor having a composition represented by the following formula (1), and a green phosphor having a composition represented by the following formula (2), or a blue light source, a green light source, and the following formula (1 ) a second white light source containing a red phosphor having a composition represented by
a red pixel, a green pixel, and a blue pixel; a red colored layer arranged corresponding to the red pixel; a green colored layer arranged corresponding to the green pixel; a color filter having a blue colored layer;
(Meth)acryloyl group, vinyl group, epoxy group, oxetanyl group, alkoxysilyl group, alkoxyl group, carboxyl group, derived from a cross-linking agent containing two or more cross-linkable groups per molecule of at least one selected from the group of isocyanate groups a display panel including an alignment film having a crosslinked structure that
has
The chromaticity point of red light emitted from the first white light source or the second white light source and obtained by passing through the red colored layer, the chromaticity point of green light obtained by passing through the green colored layer, A display device in which the chromaticity coordinates of the CIE color system calculated from the chromaticity point of the blue light obtained by passing through the blue colored layer satisfy the following equation.
Rx=0.035 cos(2πθ)+0.690,
Ry=0.035 sin(2πθ)+0.295,
Gx=0.055 cos(2πθ)+0.185,
Gy=0.055 sin(2πθ)+0.760,
Bx=0.030 cos(2πθ)+0.145,
By=0.030 sin(2πθ)+0.055
(However, θ represents a numerical value of 0 or more and less than 1)

(In formula (1), m, a, b, and c are each independently 0<m≦0.2, 1.6≦a≦2.4, m+b=1, 4.8≦c≦7. 2.)

(In formula (2), a, b, c, d, and e are 0<a≦0.2, 5.6<b≦5.99, 0.01≦c<0.4, 0.01≦c<0.4, and 0.6<b≦5.99, respectively. 01≦d<0.4 and 7.6<e≦7.99 are satisfied.) A first white light source containing a blue light source, a red phosphor having a composition represented by the following formula (1), and a green phosphor having a composition represented by the following formula (2), or a blue light source, a green light source, and the following formula (1 ) a second white light source containing a red phosphor having a composition represented by
a red pixel, a green pixel, and a blue pixel; a red colored layer arranged corresponding to the red pixel; a green colored layer arranged corresponding to the green pixel; a color filter having a blue colored layer;
Contains an organic solvent that is at least one selected from the group consisting of compounds represented by the following formulas (E-1) to (E-5) and has a boiling point of 180° C. or less at 1 atm. a display panel comprising an alignment film formed from a liquid crystal alignment agent;
has
The chromaticity point of red light emitted from the first white light source or the second white light source and obtained by passing through the red colored layer, the chromaticity point of green light obtained by passing through the green colored layer, A display device in which the chromaticity coordinates of the CIE color system calculated from the chromaticity point of the blue light obtained by passing through the blue colored layer satisfy the following equation.
Rx=0.035 cos(2πθ)+0.690,
Ry=0.035 sin(2πθ)+0.295,
Gx=0.055 cos(2πθ)+0.185,
Gy=0.055 sin(2πθ)+0.760,
Bx=0.030 cos(2πθ)+0.145,
By=0.030 sin(2πθ)+0.055
(However, θ represents a numerical value of 0 or more and less than 1)

(In formula (1), m, a, b, and c are each independently 0<m≦0.2, 1.6≦a≦2.4, m+b=1, 4.8≦c≦7. 2.)

(In formula (2), a, b, c, d, and e are 0<a≦0.2, 5.6<b≦5.99, 0.01≦c<0.4, 0.01≦c<0.4, and 0.6<b≦5.99, respectively. 01≦d<0.4 and 7.6<e≦7.99 are satisfied.)

(In formula (E-1), R ⁴¹ is an alkyl group having 1 to 4 carbon atoms or CH ₃ CO—, and R ⁴² is an alkanediyl group having 1 to 4 carbon atoms or —(R ⁴⁷ —O) r—R ⁴⁸ — (where R ⁴⁷ and R ⁴⁸ are each independently an alkanediyl group having 2 or 3 carbon atoms, and r is an integer of 1 to 4), and R ⁴³ is a hydrogen atom; or an alkyl group having 1 to 4 carbon atoms.)

(In formula (E-2), R ⁴⁴ is an alkanediyl group having 1 to 4 carbon atoms.)

(In formula (E-3), R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 8 carbon atoms.)

(In formula (E-4), R ⁴⁹ is a hydrogen atom or a hydroxyl group, R ⁵⁰ is a hydrocarbon group having 1 to 9 carbon atoms when R ⁴⁹ is a hydrogen atom, and when R ⁴⁹ is a hydroxyl group , a divalent hydrocarbon group having 1 to 9 carbon atoms or a divalent group having an oxygen atom between the carbon-carbon bonds.)

(In formula (E-5), R ⁵¹ and R ⁵² are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent group having an oxygen atom between the carbon-carbon bonds. ) A first white light source containing a blue light source, a red phosphor having a composition represented by the following formula (1), and a green phosphor having a composition represented by the following formula (2), or a blue light source, a green light source, and the following formula (1 ) a second white light source containing a red phosphor having a composition represented by
a red pixel, a green pixel, and a blue pixel; a red colored layer arranged corresponding to the red pixel; a green colored layer arranged corresponding to the green pixel; a color filter having a blue colored layer;
an alignment film containing at least one polymer selected from the group consisting of a styrenic polymer containing an aromatic hydrocarbon group, a (meth)acrylic polymer, polysiloxane, polyamic acid and a polyamic acid derivative; and ,
has
The chromaticity point of red light emitted from the first white light source or the second white light source and obtained by passing through the red colored layer, the chromaticity point of green light obtained by passing through the green colored layer, A display device in which the chromaticity coordinates of the CIE color system calculated from the chromaticity point of the blue light obtained by passing through the blue colored layer satisfy the following equation.
Rx=0.035 cos(2πθ)+0.690,
Ry=0.035 sin(2πθ)+0.295,
Gx=0.055 cos(2πθ)+0.185,
Gy=0.055 sin(2πθ)+0.760,
Bx=0.030 cos(2πθ)+0.145,
By=0.030 sin(2πθ)+0.055
(However, θ represents a numerical value of 0 or more and less than 1)

(In formula (1), m, a, b, and c are each independently 0<m≦0.2, 1.6≦a≦2.4, m+b=1, 4.8≦c≦7. 2.)

(In formula (2), a, b, c, d, and e are 0<a≦0.2, 5.6<b≦5.99, 0.01≦c<0.4, 0.01≦c<0.4, and 0.6<b≦5.99, respectively. 01≦d<0.4 and 7.6<e≦7.99 are satisfied.) 4. The display device according to any one of claims 1 to 3, wherein the concentration of the coloring material contained in each of the red colored layer, the green colored layer, and the blue colored layer is 10% or more and less than 50%. The coloring material contained in the red colored layer contains at least one selected from diketopyrrolopyrrole, anthraquinone, azo, isoindoline, methine, xanthene, and dioxazine series,
The colorant contained in the green colored layer contains at least one selected from phthalocyanine, azo, quinophthalone, coumarin, merocyanine, squarylium, and azomethine,
5. The display device according to any one of claims 1 to 4, wherein the coloring material contained in the blue colored layer contains at least one selected from phthalocyanine, dioxazine-based, triarylmethane-based, xanthene, and anthraquinone. 4. The display device according to claim 1, further comprising a protective film on said color filter. 4. A display device according to any one of claims 1 to 3, further comprising photospacers on the color filters. 4. A display device according to any preceding claim, further comprising bead spacers on said color filters. Each of the red pixel, the green pixel, and the blue pixel includes a switching element and a pixel electrode electrically connected to the switching element, and the switching element is covered with an organic interlayer insulating film. The display device according to any one of claims 1 to 3. 10. The display device according to claim 9, wherein said color filter is arranged on said organic interlayer insulating film. forming an array substrate provided with pixel electrodes respectively corresponding to red pixels, green pixels, and blue pixels;
A color filter having a red colored layer arranged corresponding to the red pixel, a green colored layer arranged corresponding to the green pixel, and a blue colored layer arranged corresponding to the blue pixel is provided. forming a facing substrate,
forming a coating film of a liquid crystal aligning agent on at least one of the array substrate and the counter substrate;
baking the coating film of the liquid crystal aligning agent in a temperature range of 200 ° C. or less to form an alignment film;
A method of manufacturing a display device comprising: forming a coating film of the first curable composition on the color filter;
exposing and developing the coating film of the first curable composition;
12. The method of manufacturing a display device according to claim 11, comprising thermally curing the coating film of the first curable composition after the development to form a protective film. forming a coating film of a second curable composition on at least one of the array substrate and the counter substrate;
exposing and developing the coating film of the second curable composition,
13. The method of manufacturing a display device according to claim 11, comprising baking the developed coating film of the second curable composition in a temperature range of 200[ deg.] C. or less to form a photospacer. forming a coating film of a third curable composition on the array substrate ;
exposing and developing the coating film of the third curable composition;
12. The method of manufacturing a display device according to claim 11, comprising baking the developed coating film of the third curable composition in a temperature range of 200[ deg.] C. or less to form an interlayer insulating film. A colored curable composition used for producing the color filter according to any one of claims 1 to 3. A liquid crystal aligning agent used for manufacturing the display device according to claim 1 . A curable composition for forming a protective film used for manufacturing the display device according to claim 12 . A curable composition for forming a photospacer used for manufacturing the display device according to claim 13 . A curable composition for forming an interlayer insulating film used for manufacturing the display device according to claim 14 .

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