JP2017049409A - Liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display that has a wide color reproduction range, prevents display unevenness, and has good display characteristics.SOLUTION: There is provided a liquid crystal display 20 comprising: a backlight 4 that includes a white LED in which colors are mixed by combining a blue LED, red phosphor, and green phosphor; and a color filter 7 that includes a plurality of colors of colored pixels including red pixels, green pixels, and blue pixels on a transparent substrate 15. The emission spectrum of the white LED has a first peak wavelength in a range of 440 nm or more and 470 nm or less, second peak wavelength in a range of 520 nm or more and 550 nm or less, and third peak wavelength, fourth peak wavelength, and fifth peak wavelength in a range of 610 nm or more and 700 nm or less; and a red photosensitive coloring composition used in formation of the red pixels includes C.I. Pigment Red 254 in an amount of 40 wt% or more and 90 wt% or less based on the total organic pigment in the solid content.SELECTED DRAWING: Figure 1

Description

The present invention relates to a liquid crystal display device comprising a backlight using LEDs and a color filter.

In recent years, color liquid crystal display devices are often used in smartphones and tablets using LEDs as light sources in addition to liquid crystal color televisions and liquid crystal display device-integrated notebook personal computers, and have formed a large market.

FIG. 1 shows a schematic cross-sectional view of a liquid crystal display device 20 using LEDs as light sources. The liquid crystal display device 20 includes a liquid crystal panel 5 including a color filter substrate 1, a liquid crystal layer 2, and a TFT array substrate 3, and a backlight 4 provided on the back surface of the liquid crystal panel 5.

Although alignment films are present on the surfaces of the color filter substrate 1 and the array substrate 3 that are in contact with the liquid crystal layer 2, they are not shown. Although a black matrix exists in the same layer as the color filter 7, it is not shown. An overcoat 8 made of a transparent resin is laminated on the color filter 7 (lower layer in FIG. 1). Photo spacers are formed on the overcoat 8 to keep the distance between the color filter substrate 1 and the array substrate 3 constant when the color filter substrate 1 and the array substrate 3 are bonded together via the liquid crystal layer 2. However, the illustration is omitted. The array substrate 3 includes an array unit 16 including TFTs (transistors).

As a method of installing the LEDs in the backlight 4, a method of obtaining a surface light source by converting light into a planar shape using a light-transmitting light guide plate 13 such as an acrylic plate disposed on a side surface as shown in FIG. In addition to the light method, a method (direct method) in which the liquid crystal element is disposed directly under the back surface is employed. For applications that require high brightness, the direct light system is suitable, and for applications that require thinning, the edge light system is suitable.

The edge light method will be described. The backlight 4 includes white LEDs 9 and 10 as edge lights on both sides of a light guide plate 13 formed of acrylic resin or the like. White light emitted from the white LED is reflected by the reflecting plate 14 and emitted to the observer side via the light guide plate 13. Note that illustration of optical elements such as a prism sheet and an increased reflection film is omitted.

A structural example of a white LED is shown in FIG. The white LED shown here is a surface-mounted LED. (In addition to the surface mount type, an insertion type is also used). In the surface-mounted LED, a light-emitting element 52 is attached to the bottom surface of a concave portion of a light-emitting element mounting housing 51 having a concave portion opened upward, and a light-emitting phosphor 53 is placed on the light-emitting element 52. The dispersed translucent resin 54 is covered. The upper electrode of the light emitting element 52 is connected to the first external electrode 56 by the first wire 55, and the lower electrode is connected to the second external electrode 58 by the second wire 57. The light reflecting material 59 is coated on the inner surface of the concave portion of the light emitting element mounting casing 51. The light emitting element 52 has a blue light emitting layer made of a compound semiconductor, and serves as an excitation light source for a red light emitting phosphor, a green light emitting phosphor, or a yellow light emitting phosphor.
(Hereinafter, the light emitting phosphor is abbreviated as phosphor as appropriate)

Nitride-based compound semiconductors (In _i Ga _j Al _k N, where 0 ≦ i, 0 ≦ j, 0 ≦ k, i + j + k = 1) include various types of materials including InGaN and GaN doped with various impurities. There is something. This light emitting element is formed by growing a semiconductor such as InGaN or GaN on a substrate by MOCVD or the like.

Examples of the structure of the nitride compound semiconductor include a homostructure having a MIS junction, a PI junction, and a PN junction, a heterostructure, and a double heterostructure. The emission wavelength of this nitride semiconductor can be variously selected depending on the material and the degree of mixed crystal. Moreover, it can also be set as the single quantum well structure and multiquantum well structure which formed the semiconductor active layer with the thin film which produces a quantum effect.

As a white LED, a two-wavelength LED and a three-wavelength LED are given as typical pseudo-white LEDs. A two-wavelength LED is obtained by mixing light emitted from a blue LED through a phosphor such as YAG (yttrium, aluminum, garnet) and has a peak wavelength of emission intensity derived from a blue LED in a wavelength range of 440 nm to 470 nm. And has a peak wavelength of emission intensity derived from the yellow phosphor in a wavelength range of 520 nm to 560 nm. FIG. 6 shows an example of light emission characteristics of the two-wavelength white LED.

On the other hand, in the three-wavelength LED, part of the blue light emitted from the near-ultraviolet or blue LED is transmitted through the phosphor layer, and the rest is absorbed by the green phosphor and the red phosphor, and converted into green and red light, respectively. An example is given. This white LED has a peak wavelength of emission intensity derived from a blue LED in a wavelength range of 440 nm to 470 nm, and has emission intensity derived from a green phosphor and a red phosphor in a wavelength range of 520 nm to 560 nm and 600 nm to 700 nm. Has a peak wavelength.

Many conventional display devices comply with sRGB (IEC 61966-2-1), which is an international standard for a color space (wide color reproduction range). However, there is a demand for a display device corresponding to the AdobeRGB standard (hereinafter abbreviated as Adobe standard) that requires higher color reproducibility than sRGB due to the further expansion of the color gamut, that is, the demand for high color reproducibility. It is growing. The Adobe standard is a definition of color reproducibility proposed by Adobe Systems. In the Adobe standard, the three primary colors are defined as follows for chromaticity coordinates (x, y) in the XYZ color system.
Red: x = 0.64; y = 0.34
Green: x = 0.21; y = 0.71
Blue: x = 0.15; y = 0.06

Standards for evaluating color reproducibility include NTSC (National Television System Committee) ratio in addition to sRGB and Adobe standards. The NTSC ratio usually evaluates color reproducibility by a ratio to the area of a triangle formed by chromaticity coordinates of red, green, and blue determined by NTSC. In order to comply with the Adobe standard, it is necessary to satisfy at least 90% as the NTSC ratio.

Also in color liquid crystal display devices using LEDs as light sources, the demand for display performance is increasing year by year. In particular, with the rapid spread of smartphones in recent years, display performance with higher color reproducibility and no display unevenness is required for viewing movies, photographs, and the like.

As a precedent example of high color reproducibility by an LED backlight, Patent Document 1 discusses high color reproducibility of a green pixel, and Patent Document 2 proposes using a three-color LED. In either case, an effect is seen in improving color reproducibility, but compatibility with Adobe is not shown, and display unevenness has not been studied.

JP 2003-238898 A Patent No. 531321

The present invention has been made to solve the above-described problems, and realizes a liquid crystal display device capable of obtaining high color reproducibility and free from display unevenness.

In order to solve the above-mentioned problem, the invention described in claim 1 is directed to a backlight including a white LED that is a mixture of a blue LED, a red phosphor, and a green phosphor, and a red pixel, green on a transparent substrate. A liquid crystal display device comprising a color filter comprising a plurality of colored pixels including a pixel and a blue pixel, wherein the emission spectrum of the white LED has a first peak wavelength of 440 nm to 470 nm and a first peak wavelength of 520 nm to 550 nm. 2 having a peak wavelength of 610 nm to 700 nm, a third peak wavelength, a fourth peak wavelength, and a fifth peak wavelength,
And the organic pigment in the red photosensitive coloring composition used for formation of the red pixel of the color filter is at least C.I. I. Pigment Number 254, and 40 wt% or more and 90 wt% or less of the total organic pigment in the solid content of the red photosensitive coloring composition is C.I. I. Pigment number 254,
The chromaticity coordinates (x, y) in the XYZ color system of the liquid crystal display device are such that the red pixel has four points (0.630, 0.320), (0.630, 0.350), (0. 650, 0.350), (0.650, 0.320), and the green pixel has four points (0.200, 0.700), (0.200, 0.720). ), (0.220, 0.720), (0.220, 0.700), and the blue pixel has four points (0.140, 0.050), (0. 140, 0.070), (0.160, 0.070), and (0.160, 0.050) are within the chromaticity coordinates connecting the liquid crystal display devices.

According to a second aspect of the present invention, an intensity value at a third peak wavelength, an intensity value at a fourth peak wavelength, an intensity value at a fifth peak wavelength of the emission spectrum of the white LED, The liquid crystal display device according to claim 1, wherein an intensity value at a peak wavelength of 1 satisfies the following (Equation 1).
1.0 ≦ Max (Intensity value at the third peak wavelength, Intensity value at the fourth peak wavelength, Intensity value at the fifth peak wavelength) / Intensity value at the first peak wavelength) ≦ 2.0
... (Formula 1)
Here, Max (A, B, C) indicates the maximum value among A, B, and C.

The invention according to claim 3 is the phosphor material according to claim 1, wherein the red phosphor is a phosphor material including a composite fluoride phosphor activated with Mn ⁴⁺ . This is a liquid crystal display device.

In the invention according to claim 4, the organic pigment in the green photosensitive coloring composition used for forming the green pixel of the color filter is at least C.I. I. Pigment number 58 and C.I. I. Pigment Number 15: 3, and 30 wt% or more and 70 wt% or less of the total organic pigment in the solid content of the green photosensitive coloring composition is C.I. I. The liquid crystal display device according to claim 1, wherein the liquid crystal display device has a pigment number of 58.

According to the present invention, it is possible to realize a liquid crystal display device that satisfies the NTSC ratio of 90% or more, has high color reproducibility conforming to the AdobeRGB standard, and has no display unevenness.

It is a cross-sectional schematic diagram of the liquid crystal display device which uses LED as a light source. It is a cross-sectional schematic diagram which shows the structural example of white LED. It is a characteristic view which shows the emission spectrum of 3 wavelength white LED used in the Example. It is a characteristic view which shows the emission spectrum of 3 wavelength white LED used by the comparative example. It is a characteristic view which shows the emission spectrum of 3 wavelength white LED used by the comparative example. It is a characteristic view which shows the example of the emission spectrum of 2 wavelength white LED.

As a result of diligent research on a liquid crystal display device including an LED backlight and a color filter, the present inventors have found that materials and characteristics are required to realize a liquid crystal display device having high color reproducibility and no display unevenness. Thus, the present inventors have found that it is necessary to match the emission spectrum of the LED backlight and the transmission spectrum of the color filter by strict selection.

Hereinafter, embodiments of the liquid crystal display device of the present invention will be described.
[overall structure]
The installation method of the white LEDs in the backlight of the liquid crystal display device of the present invention is not limited to the edge light method as shown in FIG. 1, but a direct method can also be adopted.

The structure of the white LED is not limited to the surface mount type as shown in FIG. 2, and an insertion type can also be used. The surface mount type will be described below.

In the liquid crystal display device of the present invention, a touch panel or a cover glass may be bonded to the polarizing film 11 (see FIG. 1), and the color filter substrate 1 is provided with touch electrodes for touch sensing or touch sensing functional elements. May be. A transparent electrode may be provided on the overcoat 8.

[White LED]
Since the two-wavelength white LED having the light emission characteristics as shown in FIG. 6 does not have a sharp peak in a wavelength range longer than 500 nm, the reproducibility of green and red is remarkably lowered, and a liquid crystal display device with high color reproducibility is realized. It ’s difficult.

Therefore, the liquid crystal display device according to the present invention uses a blue LED and a three-wavelength white LED obtained from a red phosphor and a green phosphor for backlight. Since the three-wavelength white LED is a mixture of two types of phosphors, it has a strong emission peak even in a wavelength region longer than 500 nm. Therefore, a liquid crystal display device having high color reproducibility can be obtained by providing a color filter substrate having a plurality of colors including a red pixel, a green pixel, and a blue pixel that match the emission spectrum of the three-wavelength white LED.

The white LED used for the backlight of the liquid crystal display device of the present invention has an emission spectrum having a first peak wavelength of 440 to 470 nm, a second peak wavelength of 520 to 550 nm, and a third peak wavelength of 610 to 700 nm. It has a peak wavelength, a fourth peak wavelength, and a fifth peak wavelength.

Further, the white LED used for the backlight of the liquid crystal display device according to the present invention has an emission spectrum having a third peak wavelength, a fourth peak wavelength, and a fifth peak wavelength in a range from 610 nm to 700 nm. The maximum value of the intensity value at the third peak wavelength, the intensity value at the fourth peak wavelength, and the intensity value at the fifth peak wavelength, and the intensity value at the first peak wavelength are as follows: Fulfill.
1.0 ≦ Max (Intensity value at the third peak wavelength, Intensity value at the fourth peak wavelength, Intensity value at the fifth peak wavelength) / Intensity value at the first peak wavelength) ≦ 2.0
... (Formula 1)
Here, Max (A, B, C) indicates the maximum value among A, B, and C.
Furthermore, it is desirable to satisfy (Formula 2).
1.2 ≦ Max (Intensity value at the third peak wavelength, Intensity value at the fourth peak wavelength, Intensity value at the fifth peak wavelength) / Intensity value at the first peak wavelength) ≦ 1.8
... (Formula 2)

The characteristics of the emission spectrum are based on the blue display chromaticity and the red display chromaticity when a color filter having a blue pixel and a red pixel, which will be described later, is combined. When the ratio of the maximum value of the third peak wavelength intensity value, the fourth peak wavelength intensity value, and the fifth peak wavelength intensity value to the first peak wavelength intensity value is less than 1.0, red reproducibility Gets worse and is perceived orange. On the other hand, when the value is larger than 2.0, the blue reproducibility deteriorates and the color is perceived as purple.

The red and green light emitting phosphors used for producing white LEDs having emission spectrum characteristics that contribute to the color reproducibility of the liquid crystal display device of the present invention are described below.

(Red light emitting phosphor)
As the red phosphor, a phosphor that is excited by primary light having an emission peak in the wavelength range of 440 to 470 nm and emits red light having an emission peak in the wavelength range of 610 to 700 nm is used.

As such a red light emitting phosphor, a composite fluoride phosphor activated with Mn ⁴⁺ is included, and the composite fluoride phosphor further comprises:
(A) A ₂ [MF ₅ ]: Mn ⁴⁺ in which A is selected from Li, Na, K, Rb, Cs, NH ₄ , and combinations thereof, and M is selected from Al, Ga, In, and combinations thereof,
(B) A ₃ [MF ₆ ]: Mn ⁴⁺ in which A is selected from Li, Na, K, Rb, Cs, NH ₄ , and combinations thereof, and M is selected from Al, Ga, In, and combinations thereof,
(C) Zn ₂ [MF ₇ ]: Mn ⁴⁺ in which M is selected from Al, Ga, In, and combinations thereof,
(D) A is selected from Li, Na, K, Rb, Cs, NH ₄ , and combinations thereof, A [In ₂ F ₇ ]: Mn ⁴⁺ ,
(E) A ₂ [MF ₆ ] where A is selected from Li, Na, K, Rb, Cs, NH ₄ and combinations thereof, and M is selected from Ge, Si, Sn, Ti, Zr and combinations thereof: Mn ⁴⁺ ,
(F) E [MF ₆ ]: Mn ⁴⁺ in which E is selected from Mg, Ca, Sr, Ba, Zn, and combinations thereof, and M is selected from Ge, Si, Sn, Ti, Zr, and combinations thereof. (G) Ba 0.65 Zr 0.35 F _2.70 : Mn ⁴⁺ : and (H) A ₃ [ZrF ₇ ]: Mn ⁴⁺ in which A is selected from Li, Na, K, Rb, Cs, NH ₄ , and combinations thereof. ,
Preferably, it comprises at least one phosphor selected from the group consisting of:
As a red light emitting phosphor that is often used at present, there is a red light emitting phosphor to which Eu ³⁺ is added, but in the near ultraviolet to blue region (370 to 480 nm) as compared with the phosphor of the present invention to which Mn ⁴⁺ is added. Does not absorb the light. Therefore, there is an unacceptable wavelength range due to scattering by the phosphor, which leads to light loss.

(Green light emitting phosphor)
As the green phosphor, a phosphor that is excited by primary light having an emission peak in a wavelength range of 360 to 460 nm and emits green light having an emission peak in a wavelength range of 520 to 560 nm is used.

Examples of such green phosphors include those composed of at least one phosphor selected from europium and manganese activated alkaline earth magnesium orthosilicate phosphors and europium activated sialon phosphors.

More specifically, as the green phosphor, for example, a divalent europium and manganese activated silicate phosphor substantially represented by the following (Chemical Formula 1), or the following (Chemical Formula 2) or (Chemical Formula 3): And europium-activated sialon phosphors substantially represented by:

[Chemical 1]
_{(Sr 2-x-y-} z-u Ba x Mg y Eu z Mn u) SiO 4 ··· ( Formula 1)
(Wherein x, y, z and u are values satisfying 0.1 <x <1.0 ≦ y <0.21, 0.05 <z <0.3, 0 ≦ u <0.04. is there)

[Chemical formula 2]
_{(Sr 3-x Eu x)} Si y Al z O v N w ··· ( Formula 2)
(Wherein x, y, z, v and w are 0 <x ≦ 3, 12 <y <14, 2 <z <3.5,
1 <v <3, 20 <w <22)

[Chemical formula 3]
(Si, Al) ₆ (O, N) ₈ : Eu _x (Chemical formula 3)
(Where x is a number satisfying 0 <x <0.3)

In addition, the phosphor substantially represented by (Chemical Formula 1) to (Chemical Formula 3) is expressed as a green-emitting phosphor or a yellow-emitting phosphor depending on the numerical values of x, y, z, v, and w in the formula. In the present specification, however, it is generally referred to as a green-emitting phosphor.

In the above (Chemical Formula 1), when x and u are within the above ranges, the wavelength of the green light emitted from the green phosphor powder is suitable as the green light constituting the white light used in the liquid crystal display device of the present invention. Have different wavelengths. Further, in (Chemical Formula 1), it is preferable that u is in the above range, since the Mn is sufficiently dissolved in the green phosphor powder, so that the luminous efficiency is increased. Furthermore, it is preferable that z in (Chemical Formula 1) is within the above range because the luminous efficiency of the green phosphor powder is increased.

In the above (Chemical Formula 2), when x, y, z, v, and w are within the above ranges, the wavelength of green light emitted from the green phosphor powder is the white light used in the liquid crystal display device of the present invention. It is suitable as the green light constituting.

In the above (Chemical Formula 3), when x is within the above range, the wavelength of the green light emitted from the green phosphor powder is suitable as the green light constituting the white light used in the liquid crystal display device of the present invention. .

As the green phosphor, one of the phosphors substantially represented by the above (Chemical Formula 1) to (Chemical Formula 3) can be used alone or in admixture of two or more. That is, the green phosphor is substantially represented by the divalent europium and manganese activated silicate phosphor substantially represented by (Chemical Formula 1) and (Chemical Formula 2) or (Chemical Formula 3). It can be composed of at least one green phosphor selected from europium activated sialon phosphors.

The method for producing the green phosphor is not particularly limited. For example, in the case of the phosphor of (Chemical Formula 1), the following method may be mentioned. First, barium carbonate (BaCO ₃ ), strontium carbonate (SrCO ₃ ), manganese carbonate (MnCO ₃ ), magnesium oxide (M
gO), europium oxide (Eu ₂ O ₃ ), and silicon dioxide (SiO ₂ ) are weighed in a predetermined amount so as to have the composition shown in (Chemical Formula 1), and these are mixed together with a sintering aid and mixed thoroughly. . This raw material mixture is put into a refractory material such as a crucible and fired at a temperature of 1100 to 1300 ° C. for about 2 to 5 hours. Thereafter, the fired product obtained is washed with pure water to remove unnecessary soluble components. Then, after passing through a pulverization step, the target green phosphor is obtained by filtration and drying. In addition, as a green fluorescent substance, the thing by the general manufacturing method other than the above, and the commercial item of the composition which satisfy | fills (Chemical formula 1)-(Chemical formula 3) can also be used.

[Color filter substrate]
Next, for a photosensitive coloring composition for producing a color filter substrate having a transmission spectrum characteristic that contributes to the color reproducibility of the liquid crystal display device of the present invention (hereinafter referred to as “photosensitivity” as appropriate), Described below.

(Red photosensitive coloring composition)
In the red coloring composition used for the color filter according to the present embodiment, C.I. I. Pigment number 254, C.I. I. It is preferable that the pigment number 254 is contained in an amount of 40 wt% to 90 wt% in the total organic pigment in the solid content of the red coloring composition. More preferably, it is 40 wt% or more and 80 wt% or less.

C. I. If the pigment number 254 is more than 90 wt% in the total organic pigment in the solid content of the red coloring composition, the red chromaticity y becomes small and the Adobe standard cannot be satisfied.

As a red coloring composition used for the color filter for liquid crystal display devices, C.I. I. Although the pigment number 177 is also generally used in many cases, since the thickness direction retardation is small, the amount used is preferably less than 40 wt% in the total organic pigment in the solid content of the red coloring composition. C. I. When the pigment number 254 is less than 40 wt% in the total organic pigment in the solid content of the red coloring composition, C.I. I. The pigment number 177 is required to be 40 wt% or more, and since the thickness direction retardation is small, the oblique visibility of the liquid crystal display device is deteriorated and unevenness occurs.

(Green photosensitive coloring composition)
In the green coloring composition used for the color filter which concerns on this embodiment, C.I. I. Pigment number 58 and C.I. I. Pigment number 15: 3, C.I. I. It is preferable that the pigment number 58 is 30 wt% or more and 70 wt% or less in the total organic pigment in the solid content of the green coloring composition.

C. I. When the pigment number 58 is less than 30 wt% of the total organic pigment in the solid content of the green coloring composition, the green chromaticity x becomes small and the Adobe standard cannot be satisfied. C. I. If the pigment number 58 is more than 70 wt% in the total organic pigment in the solid content of the green coloring composition, the green chromaticity x increases and the Adobe standard cannot be met. Furthermore, C.I. I. When the pigment number 15: 3 is not included, the curing component cannot be sufficiently added, and there is a possibility that a shape defect or the like may occur even if it conforms to the Adobe standard.

Hereinafter, modes of other parts belonging to the liquid crystal display device of the present invention will be described.
The transparent substrate for laying the color filter preferably has a certain degree of transmittance with respect to visible light, and more preferably has a transmittance of 80% or more. Generally, it may be one used in a liquid crystal display device, and a plastic substrate such as PET or a glass substrate is also used, but a glass substrate is usually used. In the case of attaching a light shielding pattern, a known method may be used in which a metal thin film such as chrome or a light shielding resin pattern is attached on a transparent substrate in advance.

Of the organic pigments that can be used in the color composition for forming the color layers of the red, green, and blue pixels of the color filter, other than the pigments specified in the claims of the present invention, red pigments, orange pigments, and green pigments Specific examples of yellow pigments, blue pigments, and purple pigments are indicated by color index numbers below.

Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 255, 264, 272, 279 and the like.

Examples of the orange pigment include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 and the like.

Examples of green pigments include C.I. I. Pigment Green 7, 10, 35, 36, 37, 59 and the like.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 139, 147, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 4, 15: 5, 16, 22, 24, 24: x, 56, 60, 61, 62, 80 and the like.

Examples of purple pigments include C.I. I. PigmentViolet 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 27, 29, 30, 32, 37, 40, 42, 50, and the like.

The pigments described above can be used alone or in combination of two or more with the organic pigments specified in the claims of the present invention.

In addition, in combination with the organic pigment used in the color filter provided in the liquid crystal display device of the present invention, an inorganic pigment is combined in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and brightness. Can also be used. Inorganic pigments include yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green and other metal oxide powders, metal sulfide powders, metal powders, etc. Can be mentioned. Furthermore, for color matching, a dye can be contained within a range that does not lower the heat resistance.

Examples of the dye include acid dyes, oil-soluble dyes, disperse dyes, reactive dyes, and direct dyes. For example, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diarylmethane dyes, triarylmethane dyes, fluorans Dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

Specific examples of the dye include, but are not limited to, the following color index numbers. C. I. Solvent Yellow 2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190, 191, C.I. I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112, 113, C.I. I. SolventRed 1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69, 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 23 , 238,239,240,241,242,243,244,245,247,248, C. I. SolventViolet 2, 8, 9, 11, 13, 14, 21, 21: 1, 26, 31, 36, 37, 38, 45, 46, 47, 48, 49, 50, 51, 55, 56, 57, 58, 59, 60, 61, C.I. I. Solvent Blue 2, 3, 4, 5, 7, 18, 25, 26, 35, 36, 37, 38, 43, 44, 45, 48, 51, 58, 59, 59: 1, 63, 64, 67, 68, 69, 70, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 124, 128, 129, 132, 136, 137, 138, 139, 143, C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, C.I. I. Solvent Brown 1, 3, 4, 5, 12, 20, 22, 28, 38, 41, 42, 43, 44, 52, 53, 59, 60, 61, 62, 63, C.I. I. Solvent Black 3, 5, 5: 2, 7, 13, 22, 22: 1, 26, 27, 28, 29, 34, 35, 43, 45, 46, 48, 49, 50, C.I. I. Acid Red 6, 11, 26, 60, 88, 111, 186, 215, C.I. I. AcidGreen 25, 27, C.I. I. Acid Blue 22, 25, 40, 78, 92, 113, 129, 167, 230, C.I. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, C.I. I. BasicGreen 3, 4, C.I. I. BasicBlue 3, 7, 9, 17, 41, 66, C.I. I. BasicViolet 1, 3, 18, 39, 66, C.I. I. Basic Yellow 11, 23, 25, 28, 41, C.I. I. DirectRed 4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149, 224, C.I. I. DirectGreen 26, 28, C.I. I. DirectBlue 71, 78, 98, 106, 108, 192, 201, C.I. I. DirectViolet 51, C.I. I. Direct Yellow 26, 27, 28, 33, 44, 50, 86, 142, C.I. I. Direct Orange 26, 29, 34, 37, 72, C.I. I. SulfurRed 5, 6, 7, C.I. I. SulfurGreen 2, 3, 6, C.I. I. SulfurBlue 2, 3, 7, 9, 13, 15, C.I. I. Sulfur Violet 2, 3, 4, C.I. I. Sulfur Yellow 4, C.I. I. VatRed 13, 21, 23, 28, 29, 48, C.I. I. VatGreen 3, 5, 8, C.I. I. VatBlue 6, 14, 26, 30, C.I. I. VatViolet 1, 3, 9, 13, 15, 16, C.I. I. Vat Yellow 2, 12, 20, 33, C.I. I. Vat Orange 2, 5, 11, 15, 18, 20, C.I. I. Azoic Coupling Component 2, 3, 4, 5, 7, 8, 9, 10, 11, 13, 32, 37, 41, 48, C.I. I. Reactive Red 8, 22, 46, 120, C.I. I. Reactive Blue 1, 2, 7, 19, C.I. I. Reactive Violet 2, 4, C.I. I. Reactive Yellow 1, 2, 4, 14, 16, C.I. I. Reactive Orange 1, 4, 7, 13, 16, 20, C.I. I. Disperse Red 4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356, C.I. I. DisperseBlue 3, 24, 79, 82, 87, 106, 125, 165, 183, C.I. I. DisperseViolet 1, 6, 12, 26, 27, 28, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64, C.I. I. Disperse Orange 13, 29, 30. These dyes can be used alone or in combination of two or more.

The transparent resin used for the coloring composition is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. If necessary, the transparent resin can be used alone or in admixture of two or more monomers or oligomers that are precursors thereof that are cured by irradiation with radiation to produce a transparent resin.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer can be obtained from (meth) acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

Examples of polymerizable monomers that can be used as a photocrosslinking agent include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide-modified trimethylolpropane tri (meth). Representative examples include various acrylic esters and methacrylic esters such as acrylate and propylene oxide-modified trimethylolpropane tri (meth) acrylate. These can be used alone or in combination of two or more, and for the purpose of keeping the photocurability properly, other polymerizable monomers and oligomers can be mixed and used as necessary.

Other polymerizable monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (Meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, Various acrylic acid esters and methacrylic acid esters such as urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) Examples include acrylamide, N-vinylformamide, acrylonitrile and the like. Also about these, it can use individually or in mixture of 2 or more types.

When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the coloring composition. As photopolymerization initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3 Benzophenone compounds such as 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4- Thioxanthone compounds such as diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], Oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenyl Phosphine compounds such as phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquino Quinone compounds such as borate compounds, carbazole compounds, imidazole compounds, titanocene compounds and the like. These photopolymerization initiators can be used alone or in combination of two or more. The amount of the photopolymerization initiator used is preferably 0.5 to 50 wt%, more preferably 3 to 30 wt% based on the total solid content of the colored composition.

Further, as sensitizers, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-Dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) ) Amine compounds such as benzophenone can also be used in combination. These sensitizers can be used alone or in combination. The amount of the sensitizer used is preferably 0.5 to 60 wt%, more preferably 3 to 40 wt% based on the total amount of the photopolymerization initiator and the sensitizer.

Furthermore, the coloring composition can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-to Azine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination of two or more.

Moreover, as a thermal crosslinking agent contained as needed, a melamine resin, an epoxy resin, etc. are mentioned, for example. Examples of the melamine resin include alkylated melamine resins (methylated melamine resin, butylated melamine resin, etc.), mixed etherified melamine resins, and the like, which may be a high condensation type or a low condensation type. Examples of the epoxy resin include glycerol / polyglycidyl ether, trimethylolpropane / polyglycidyl ether, resorcin / diglycidyl ether, neopentyl glycol / diglycidyl ether, 1,6-hexanediol / diglycidyl ether, ethylene glycol (polyethylene). Glycol) and diglycidyl ether. Any of these may be used alone or in admixture of two or more.

The coloring composition can contain an organic solvent as necessary. Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination.

The pixel may be formed on the transparent substrate by any known method such as a photolithography method, a printing method, an ink jet method, and an etching method. However, in consideration of high definition, controllability of spectral characteristics, reproducibility, etc., the photolithography method is preferable, and a colored composition in which a pigment is dispersed in a suitable solvent together with a photoinitiator and a polymerizable monomer in a transparent resin. Is formed on a transparent substrate to form a colored layer, and the process of forming a pixel of one color by pattern exposure and development of the colored layer is repeated for each color to produce a color filter. There are various methods such as a mill base, three rolls, and a jet mill for dispersing the pigment as the colorant and the transparent resin, and the method is not particularly limited.

A series of steps such as photolithography is performed by changing the photosensitive coloring composition and pattern and repeating the necessary number of times to obtain a colored pattern in which a necessary number of colors are combined, that is, a color filter substrate having a plurality of color pixels. Can do.

Examples according to the present invention will be described together with comparative examples. The embodiment is not limited to this within the scope not departing from the gist of the present invention.

[Production of white LED]
A white LED having the structure of FIG. 2 was produced as follows.
A molten polyphthalamide resin is poured from a gate on the lower surface facing the main surface of the housing into a mold in which a pair of positive and negative external electrodes are inserted and closed, and the housing is cured. Formed. The housing has an opening that can accommodate the light emitting element, and is integrally formed so that the positive and negative external electrodes are exposed from one main surface from the bottom of the opening.

The outer lead portions of the positive and negative external electrodes exposed from the side surface of the housing are bent inward at both ends opposite to the light emitting surface. A blue LED element made of a gallium nitride compound semiconductor was die-bonded to the bottom surface of the opening formed in this way with an epoxy resin and electrically connected to each external electrode with a wire. The blue LED element emits light as the first peak wavelength in the emission spectrum of the white LED used in the present invention.

Next, a green phosphor powder having an average particle diameter of 5 μm and a red phosphor powder having an average particle diameter of 5 μm are respectively selected from the above-mentioned explanations of (red light emitting phosphor) and (green light emitting phosphor). A total of 70 wt% of these phosphor powders and 30 wt% of silicone resin were mixed to obtain a translucent resin.

The translucent resin thus obtained is filled in the housing opening and heat-treated at 70 ° C. to 150 ° C. to cure the silicone resin, and the three-wavelength white LEDs-1 to 6 having the characteristics shown in Table 1 are obtained. Obtained.

White LED obtained

The emission spectrum intensities of the white LEDs-1 and 2 are shown in FIG. 3, the emission spectrum intensities of LEDs-3 and 4 are shown in FIG. 4, and the emission spectrum intensities of LEDs-5 and 6 are shown in FIG.

In the peak wavelength column of Table 1, the first peak wavelength is 440 nm to 470 nm, the second peak wavelength is 520 nm to 550 nm, the third peak wavelength is 610 nm to 700 nm, and the fourth peak wavelength. The case where there is a peak wavelength of 5 is indicated by 〇, and the case where there is no peak within the wavelength range is indicated by ×. Further, the case where the maximum value and the first peak wavelength intensity value among the third peak wavelength intensity value, the fourth peak wavelength intensity value, and the fifth peak wavelength intensity value satisfy the above-described (Equation 1). The case where it is not satisfied is indicated as x.

[Production of color filter substrate]
(Preparation of pigment dispersion)
The following were used for the pigment used as a coloring agent for producing the coloring composition used for preparation of the color filter board | substrate of an Example and a comparative example.
Red pigment: C.I. I. Pigment Red 254 (“Ilgar Forred B-CF” manufactured by Ciba Specialty Chemicals), C.I. I. Pigment Red 177 (“CROMOPHTAL RED A2B” manufactured by Ciba Specialty Chemicals) and C.I. I. Pigment Yellow 150 (Bayer's “Funcheon First Yellow Y-5688”)

Green pigment: C.I. I. Pigment Green 58 (Dainippon Ink & Chemicals, Inc. “Phthacocyanine Green A110”), C.I. I. Pigment Yellow 138 (“PALIOTOL YELLOW K0 961HD” manufactured by BASF, and CI Pigment Blue 15: 3

Blue pigment: C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Manufacturing Co., Ltd.), C.I. I. Pigment Violet 23 (manufactured by BASF “Paliogen Violet 5890”)

A mixture of the above-described pigment, pigment derivatives 1 to 4 described later, and an acrylic resin solution, and propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent are uniformly stirred and mixed, and then zirconia beads having a diameter of 1.0 mm are used. (Eiger Japan Co., Ltd. “Mini Model M-250MKII”) was dispersed for 3 hours and then filtered through a 5 μm filter to prepare a red pigment dispersion PR-1 shown in Table 2. Similarly, the red pigment dispersion PR-2, the yellow pigment dispersion PY-1 and 2, the green pigment dispersion PG-1, the blue pigment dispersion PB-1 and 2, and the purple pigment dispersion PV shown in Table 2 are shown. -1 was produced.

Composition of pigment dispersion (wt%)

The chemical structural formulas of pigment derivatives 1 to 4 are shown below.
Chemical structural formula of pigment derivative 1 (chemical structural formula 1)
Chemical structural formula of pigment derivative 2 ... (Chemical structural formula 2)
Chemical structural formula of pigment derivative 3 ... (Chemical structural formula 3)
Chemical structural formula of the pigment derivative 4 ... (Chemical structural formula 4)

(Preparation of colored composition)
A mixture (wt%) shown in Table 3 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a red photosensitive coloring composition R-1. Similarly, red photosensitive coloring compositions R-2 to R-5, green photosensitive coloring compositions G-1 to G-6, and blue photosensitive coloring composition B-1 were prepared.

Composition of coloring composition (wt%)

In the red coloring composition of Table 3, 40 wt% or more and 90 wt% or less in the total organic pigment in the solid content is C.I. I. When the pigment number is 254, it is indicated by ◯, and when it is not in the above range, it is indicated by ×. I. Pigment number 58 and C.I. I. Pigment Number 15: 3, and 30 wt% or more and 70 wt% or less of the total organic pigment in the solid content is C.I. I. The case where the pigment number is 58 is indicated by 〇, and the case where the pigment number is not within the above range is indicated by ×.

In addition, the following materials were used for preparation of the coloring composition of Table 3. Monomer: Dipentaerythritol penta / hexaacrylate mixture (“M-402” manufactured by Toa Gosei Co., Ltd.)
Photopolymerization initiator 1: 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (manufactured by Ciba Specialty Chemicals) "Irgacure 379"),
Photopolymerization initiator 2: Etanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) ("N-1919" manufactured by ADEKA Corporation)
Additive: “BYK-379” manufactured by Big Chemie

(Production of black composition)
A black photosensitive resin composition for producing a black matrix was produced as follows. Resin: 1.89 g of dipentaerythritol penta / hexaacrylate mixture (“KAYARDADDHA” manufactured by Nippon Kayaku Co., Ltd.) with respect to 12.1 g of V259-ME (manufactured by Nippon Steel Chemical Co., Ltd., solid content 50.0 wt%), photoradical 0.63 g of a polymerization initiator (ADEKA “NCI-831”), 0.66 g of a 1 wt% propylene glycol monomethyl acetate solution of a surface conditioning agent (“BYK-323” manufactured by Big Chemie), a carbon black dispersion (solid content 22) .7 wt%) 32.14 g, 0.66 g of 10 wt% propylene glycol monomethyl ether acetate solution of silane coupling agent (Shin-Etsu Chemical “KBE-9007”), thermal radical polymerization initiator (“V-59 manufactured by Wako Pure Chemical Industries, Ltd.) ]) 0.13 g and propylene glycol monomethyl ether acetate Thoroughly stirred with 51.79G, to give a black photosensitive resin composition (solid content 13.39wt%, carbon black pigment concentration 45.57wt%).

(Preparation of photosensitive resin composition for overcoat formation)
The photosensitive resin composition used for overcoat was produced as follows.
In a round bottom flask equipped with a stirrer and a condenser, 200 parts of trisphenolmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EPPN-503, epoxy equivalent 200, softening point 83 ° C.), 72 parts of acrylic acid, methyl 0.2 part of hydroquinone and 169.1 parts of propylene glycol monomethyl ether acetate were charged, heated to 90 ° C. and dissolved. Next, the mixture was cooled to 60 ° C., charged with 1.2 parts of triphenylphosphine, reacted at 95 ° C. for 32 hours, charged with 112.6 parts of tetrahydrophthalic anhydride, and reacted at 95 ° C. for 15 hours to obtain a binder polymer A. It was.

20.8 g of the binder polymer solution A obtained above, photopolymerizable compound: 10.9 g of dipentaerythritol hexaacrylate (KAYARD DPHA manufactured by Nippon Kayaku), photopolymerization initiator: OXE-02 (manufactured by Ciba Specialty Chemicals) ) 3.2 g, Surfactant: BYK-170 (solid content 30 wt%) 0.3 g (manufactured by BYK Chemie), solvent: propylene glycol monomethyl ether acetate 64.8 g is mixed to form a photosensitive resin composition for overcoat formation I got a thing.

(Preparation of photosensitive resin composition for photospacer)
The photosensitive resin composition used for photospacer formation was produced as follows.
In a separable flask, 686 g of propylene glycol monomethyl ether acetate, 332 g of glycidyl methacrylate and 6.6 g of azobisisobutyronitrile were added and heated at 80 ° C. for 6 hours in a nitrogen atmosphere to prepare a resin solution. Next, 168 G of acrylic acid, 0.05 g of methoquinone and 0.5 g of triphenylphosphine are added to the resin solution, and heated at 100 ° C. for 24 hours while blowing air to produce an acrylic acid-added resin solution. Further, 186 g of tetrahydrophthalic anhydride was added to the resulting acrylic acid-added resin solution and heated at 70 ° C. for 10 hours to obtain a binder polymer B solution.
200 g of the obtained binder polymer B solution, photopolymerizable monomer: 100 g of dipentaerythritol hexaacrylate, photopolymerization initiator: 100 g of OXE-02 (manufactured by Ciba Specialty Chemicals), 450 g of solvent (propylene glycol monomethyl ether acetate) The mixed photosensitive resin composition for photospacers was obtained.

(Production of black matrix)
Using a spin coater, the number of revolutions was adjusted so that the film thickness after baking was 1.50 μm, and a coating film of the above black composition was formed on a glass substrate (“EAGLE XG” manufactured by Corning). After drying, it was pre-baked on a hot plate at 90 ° C. for 1 minute. Next, the black coating film was irradiated with 100 mJ / cm ² of ultraviolet light using a super high pressure mercury lamp (illuminance 26 mW / cm ² ) through a photomask having a predetermined pattern. Then, it developed with 2.5 wt% sodium carbonate aqueous solution, and baked for 20 minutes in 230 degreeC clean oven, and produced the black matrix on the glass substrate.

(Production of color filter substrate)
First, a coating film of the red coloring composition R-1 shown in Table 3 was formed on the substrate on which the black matrix was produced by spin coating. After drying, through a photomask having a predetermined pattern corresponding to the opening of the black matrix, ultraviolet light is applied to the red photosensitive resin composition coating film at 100 mJ / using an ultrahigh pressure mercury lamp (illuminance 26 mW / cm ² ). Irradiated cm ² . Subsequently, development was performed with a 2.5 wt% aqueous sodium carbonate solution, and baking was performed in a clean oven at 230 ° C. for 20 minutes to form red pixels on the substrate on which the black matrix was produced. The same operation was performed using the green coloring composition G-1 and the blue coloring composition B-1 in Table 3 to form green pixels and blue pixels. Further, a coating film of the above-mentioned photosensitive resin composition for overcoat formation is formed, and after drying, the coating film of the overcoat is formed using a super high pressure mercury lamp (illuminance 26 mW / cm ² ) through a photomask having a predetermined pattern. Were irradiated with 100 mJ / cm ² of ultraviolet light. Subsequently, development was performed with a 2.5 wt% sodium carbonate aqueous solution, and baking was performed in a clean oven at 230 ° C. for 30 minutes to form an overcoat. In the same manner as the overcoat, a photospacer was formed using the above-described photosensitive resin composition for photospacer to obtain a color filter substrate CF-1.

Color filter substrates CF-1 to 10 shown in Table 4 were obtained by the same method as above.

Obtained color filter substrate

[Production of liquid crystal display devices]
Table 5 shows a combination of the edge-light type backlight having the white LEDs-1 to LED-6 in Table 1, the color filter substrates CF-1 to CF-10 in Table 4, and a separately prepared TFT array substrate. The liquid crystal display devices LCD-1 to LCD-15 shown were produced.

[Evaluation of liquid crystal display devices]
The resulting liquid crystal display device was measured for chromaticity and brightness of red pixels, green pixels, and blue pixels using a microspectrophotometer OSP-2000 (manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 5. The chromaticity coordinates (x, y) of the red pixel are 4 points (0.630, 0.320), (0.630, 0.350), (0.650, 0.350) and (0.650, 0). .320) in the chromaticity coordinates, the red pixel display is indicated by ◯, and the others are indicated by ×. The chromaticity coordinates (x, y) of the green pixel are 4 points (0.200, 0.700), (0.200, 0.720), (0.220, 0.720) and (0.220, 0). .700) is within the chromaticity coordinates, the green pixel display is indicated by ◯, and the others are indicated by ×. The chromaticity coordinates (x, y) of the blue pixel are 4 points (0.140, 0.050), (0.140, 0.070), (0.160, 0.070) and (0.160, 0). .050), the blue pixel display is indicated by ◯, and the others are indicated by ×. Further, the obtained liquid crystal display device was observed under white fluorescent light, and a black and white flag pattern was displayed to evaluate display unevenness. The results are shown in Table 5.

Summary of Examples 1-5 and Comparative Examples 1-10

In Examples 1, 2, 3, 4, and 5, a liquid crystal display device suitable for the conditions specified by the present invention, sufficiently satisfying the NTSC ratio of 90% or more, conforming to the Adobe standard, and having no display unevenness is obtained. Obtained.

As shown in Comparative Example 1 in Table 5, when the second peak wavelength is shorter than 520 nm (see LED-3 in Table 1), the chromaticity x of the green pixel becomes small. Further, as shown in Comparative Example 2, when it was longer than 550 nm (see LED-4 in Table 1), the chromaticity x of the green pixel was large, y was small, and the NTSC ratio was less than 80%. Thus, neither Comparative Example 1 nor 2 was able to meet the Adobe standard.

As shown in Comparative Example 3 in Table 5, the maximum value / first peak wavelength intensity value of the third peak wavelength intensity value, the fourth peak wavelength intensity value, and the fifth peak wavelength intensity value is 2. When it is larger than 0 (see LED-5 in Table 1), the chromaticity x of the red pixel becomes large, and as shown in Comparative Example 4, when it is smaller than 1.0 (see LED-6 in Table 1), The chromaticity x became small, and neither Comparative Example 3 nor 4 was able to meet the Adobe standard.

In Comparative Example 5 in Table 5, CF-3 is used, and therefore R-3 is used (see Table 4). In R-3, C.I. I. The ratio of pigment number 254 (ie, PR-2, see Table 2) is as shown in Table 3.
13.6 / (13.6 + 26.4) × 100 wt% ≈34 wt%
When the amount is less than 40 wt%, the chromaticity y of the red pixel is increased, and the Adobe standard cannot be satisfied.

In Comparative Example 6 in Table 5, CF-4 is used, and therefore R-4 is used (see Table 4). In R-4, C.I. I. The ratio of pigment number 254 (ie, PR-2, see Table 2) is as shown in Table 3.
16.9 / (16.9 + 1.1) × 100 wt% ≈94 wt%
In addition, the chromaticity y of the red pixel is smaller than 90 wt%, and the Adobe standard cannot be satisfied.

In Comparative Example 7 in Table 5, display unevenness occurred. This is because Comparative Example 7 uses CF-5 and therefore R-5 (see Table 4), but R-5 contains C.I. I. The ratio of pigment number 177 (ie PR-1, see Table 2) is as shown in Table 3.
12.8 / (12.8 + 7.0 + 5.3) × 100 wt% ≈51 wt%
This is due to the fact that it is more than 40 wt% and the phase difference of the red pixel is small.

In Comparative Example 8 in Table 5, CF-8 is used, and thus G-4 is used (see Table 4). In G-4, C.I. I. The ratio of pigment number 58 (ie PG-1, see Table 2) is as shown in Table 3.
9.6 / (9.6 + 16.0 + 14.4) × 100 wt% ≈24 wt%
And less than 30 wt%, the chromaticity x of the green pixel becomes small, and the Adobe standard cannot be met.

In Comparative Example 9 in Table 5, CF-9 is used, and thus G-5 is used (see Table 4). In G-5, C.I. I. The ratio of pigment number 58 (ie PG-1, see Table 2) is as shown in Table 3.
40.2 / (40.2 + 11.0 + 3.9) × 100 wt% ≈73 wt%
In other words, the chromaticity x of the green pixel is larger than 70 wt%, and the Adobe standard cannot be satisfied.

In Comparative Example 10 of Table 5, CF-10 is used, and thus G-6 is used (see Table 4). However, in G-6, C.I. I. Pigment number 1
Since 5: 3 (that is, PB-1, see Table 2) was not contained, display unevenness occurred. This is because the green color pixel has a poor shape and there is a light color area in the green pixel.

DESCRIPTION OF SYMBOLS 1 ... Color filter substrate 2 ... Liquid crystal layer 3 ... TFT array substrate 4 ... Backlight 5 ... Liquid crystal panel 7 ... Color filter 8 ... Overcoat 9, 10 ... White LED
DESCRIPTION OF SYMBOLS 11 ... Polarizing film 12 ... Adhesive layer 13 ... Light guide plate 14 ... Reflecting plate 15 ... Substrate 16 ... TFT array part 17 ... Substrate 20 ... Liquid crystal display device 51 .. Light emitting element mounting casing 52... Light emitting element 53... Light emitting phosphor 54 .. Translucent resin 55... First wire 56 ... First external electrode 57. Two wires 58 ... second external electrode 59 ... light reflecting material 60 ... white LED

Claims (4)

A backlight having a white LED mixed with a combination of a blue LED, a red phosphor and a green phosphor, and a color filter having a plurality of colored pixels including a red pixel, a green pixel and a blue pixel on a transparent substrate. In the liquid crystal display device, the emission spectrum of the white LED has a first peak wavelength of 440 nm to 470 nm, a second peak wavelength of 520 nm to 550 nm, a third peak wavelength of 610 nm to 700 nm, and Having a peak wavelength of 4, as well as a fifth peak wavelength,
And the organic pigment in the red photosensitive coloring composition used for formation of the red pixel of the color filter is at least C.I. I. Pigment Number 254, and 40 wt% or more and 90 wt% or less of the total organic pigment in the solid content of the red photosensitive coloring composition is C.I. I. Pigment number 254,
The chromaticity coordinates (x, y) in the XYZ color system of the liquid crystal display device are such that the red pixel has four points (0.630, 0.320), (0.630, 0.350), (0. 650, 0.350), (0.650, 0.320), and the green pixel has four points (0.200, 0.700), (0.200, 0.720). ), (0.220, 0.720), (0.220, 0.700), and the blue pixel has four points (0.140, 0.050), (0. 140, 0.070), (0.160, 0.070), and (0.160, 0.050) within the chromaticity coordinates connecting the liquid crystal display devices. The intensity value at the third peak wavelength, the intensity value at the fourth peak wavelength, the intensity value at the fifth peak wavelength, and the intensity value at the first peak wavelength of the emission spectrum of the white LED are as follows: The liquid crystal display device according to claim 1, wherein (Formula 1) is satisfied.
1.0 ≦ Max (Intensity value at the third peak wavelength, Intensity value at the fourth peak wavelength, Intensity value at the fifth peak wavelength) / Intensity value at the first peak wavelength) ≦ 2.0
... (Formula 1)
Here, Max (A, B, C) indicates the maximum value among A, B, and C. The liquid crystal display device according to claim 1, wherein the red phosphor is a phosphor material including a composite fluoride phosphor activated with Mn ⁴⁺ . The organic pigment in the green photosensitive coloring composition used for forming the green pixel of the color filter is at least C.I. I. Pigment number 58 and C.I. I. Pigment Number 15: 3, and 30 wt% or more and 70 wt% or less of the total organic pigment in the solid content of the green photosensitive coloring composition is C.I. I. The liquid crystal display device according to claim 1, wherein the liquid crystal display device has a pigment number of 58.