JP2012150457A - Color filter substrate and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter substrate having an excellent white balance, having high transmission factor and contrast ratio, and having a wide color reproduction range.SOLUTION: A four-color filter substrate includes red pixels, green pixels, blue pixels and forth color pixels. The red pixel includes C.I. pigment red 254, the green pixel includes at least either one type of C.I. pigment green 7, C.I. pigment green 36, or C.I. pigment green 58, the blue pixel includes C.I. pigment blue 15:6, and the fourth color pixel includes a pigment and a resin component. The pigment concentration of the entire solid component in the fourth color pixel is 0.3 to 3 mass% and a CIE 1931 standard colorimetric system chromaticity (Y) of the fourth color pixel measured by using a C-light source is 70≤Y≤99.

Description

  The present invention relates to a color filter substrate and a liquid crystal display device used for a color liquid crystal display device and the like.

  Liquid crystal display devices are used in various applications such as televisions, notebook computers, personal digital assistants, smartphones, and digital cameras, taking advantage of characteristics such as light weight, thinness, and low power consumption.

  A color filter substrate is a member necessary for color display of a liquid crystal display device, and generally has a three-color pixel of a red pixel, a green pixel, and a blue pixel finely patterned (Patent Document 1, etc.) ). White is obtained by additive color mixing of red, green and blue pixels.

  In recent years, a four-color filter substrate has been proposed as a method for improving the transmittance of a liquid crystal display device. For example, Patent Document 2 proposes a four-color filter substrate having white pixels in addition to red, green, and blue pixels. The white pixel does not contain a colorant and is transparent, and the transmittance is improved by using the white light from the light source as it is. In this method, a transparent white pixel is formed using a resin composition containing a polymerizable polymer, a cationic polymerizable compound, and a thermosensitive acid generator.

  On the other hand, Patent Document 3 proposes a four-color filter substrate having cyan pixels in addition to red, green, and blue pixels, and the chromaticity coordinates of the cyan pixels are x ≦ 0.164 and y ≧ 0.453. It is described.

JP 2004-309537 A JP 11-295717 A JP 2007-121325 A

  In patent document 1, since it is a 3 color filter substrate, there exists a subject that the transmittance | permeability is low. If a four-color color filter substrate is manufactured by combining the white pixel of Patent Document 1 and the red green blue pixel of Patent Document 2, the white pixel chromaticity and the additive color mixture chromaticity of the red green blue pixel are the same. It is expected to be. However, when this combination method is actually examined, the chromaticity of the red, green, and blue pixels is extremely limited, and there is a concern that the transmittance of the color filter substrate may decrease and the color reproduction range may decrease. Is done.

  In Patent Document 2, in order to obtain a brighter white, it is necessary to use not only white pixels but also white by additive color mixture of red, green, and blue pixels. Here, since the white pixel is transparent, the chromaticity of the white pixel is considered to be the same as the light source chromaticity. However, it is very difficult to make the additive color mixture chromaticity of the red, green, and blue pixels the same as the light source chromaticity. If the chromaticity of the white pixel and the additive color mixture chromaticity of the red, green, and blue pixels do not match, the white balance will be poor.

  Further, in Patent Document 3, the fourth color cyan pixel takes into account the white balance due to the additive color mixture of the four colors, and there is no description or suggestion regarding the improvement of the white pixel or the transmittance. This is because, when the CIE 1931 color system chromaticity (Y) of the cyan pixel is calculated from the chromaticity (x, y) of the cyan pixel and the transmission spectrum of Patent Document 3, Y is estimated to be 20-40. Therefore, in this method, since the transmittance of the fourth color cyan pixel is considerably low, it cannot be called a white pixel, and the improvement in transmittance as in Patent Document 2 cannot be expected.

  In view of the above prior art, the present invention aims to improve the white balance by matching the additive color mixture chromaticity of red, green, and blue pixels with the chromaticity of white pixels without reducing the transmittance of the color filter substrate. To do.

  Therefore, the present inventors do not match the additive color mixture chromaticity of the red, green, and blue pixels with the white pixel chromaticity, which is very difficult, but instead changes the white pixel chromaticity to the additive color mixture of the red, green, and blue pixels. Inspired to match. However, it is also difficult to unilaterally match the white pixel chromaticity to the additive color mixture chromaticity of the red, green, and blue pixels, so that the additive color mixture chromaticity of the red, green, and blue pixels can be easily matched to the white pixel chromaticity. In addition, we can walk both sides.

In order to solve the above problems, the present invention has the following configuration.
1. In a four-color filter substrate having a red pixel, a green pixel, a blue pixel, and a fourth color pixel, the red pixel is a C.I. I. Pigment Red 254 and green pixels are C.I. I. Pigment green 7, C.I. I. Pigment green 36, or C.I. I. Pigment Green 58 is contained, and the blue pixel is C.I. I. Pigment Blue 15: 6, the fourth color pixel contains a colorant and a resin, and the colorant concentration in the total solid content of the fourth color pixel is 0.3 to 3% by mass. And the CIE1931 color system chromaticity (Y) of the pixel of the fourth color measured using the C light source is
70 ≦ Y ≦ 99
A color filter substrate characterized by the above.
2. The fourth color pixel contains a pigment as a colorant, and the pigment is C.I. I. Pigment Blue (PB) 15, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, PB60, C.I. I. Pigment violet (PV) 19, PV23, PV37, C.I. I. 2. The color filter substrate according to 1, wherein the color filter substrate is one or more selected from pigment red (PR) 149, PR166, PR177, PR179, PR209, and PR254.
3. The fourth color pixel contains an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator as a resin, and the weight mixing ratio of the alkali-soluble resin and the photopolymerizable monomer is 50:50 to 20:80. 3. The color filter substrate as described in 1 or 2 above.
4). The photopolymerizable monomer is composed of a polymerizable monomer A having a solid content acid value in the range of 0 to 50 mgKOH / g and a polymerizable monomer B having a solid content acid value in the range of 50 to 150 mgKOH / g, 4. The color filter substrate according to item 3, wherein the acid content of the alkali-soluble resin is in the range of 50 to 150 mgKOH / g.
5. The area of a triangle connecting the CIE 1931 color system chromaticity (x, y) of the red, green, and blue pixels measured using a C light source connects NTSC standard chromaticity (x, y) 3 The color filter substrate according to any one of claims 1 to 4, wherein the color filter substrate is 65 to 100% of a square area.
6. A liquid crystal display device comprising the color filter substrate according to item 1-5.

In the four-color filter substrate of the present invention, since the fourth color pixel contains the appropriate amount of the colorant, the additive color mixture chromaticity of the red, green, and blue pixels and the white pixel without reducing the transmittance of the color filter substrate. The white chromaticity can be matched and the white balance can be improved.

4 is a transmission spectrum of red, blue, green, and fourth color pixels of the color filter of Example 1. FIG. 7 is a transmission spectrum of red, blue, green, and fourth color pixels of the color filter of Comparative Example 2; 7 is a transmission spectrum of red, blue, green, and fourth color pixels of the color filter of Example 6. FIG.

  The color filter substrate of the present invention is a four-color filter substrate having a red pixel, a green pixel, a blue pixel, and a fourth color pixel, wherein the fourth color pixel contains a colorant and a resin component, The CIE 1931 color system chromaticity (Y) measured using the C light source of the fourth color pixel, wherein the colorant concentration in the total solid content in the color pixel is 0.3 to 3% by mass ) Is 70 ≦ Y ≦ 99.

  That is, according to the present invention, the chromaticity of the red-green-blue pixel is adjusted by setting the colorant concentration of the fourth color pixel within the above range and the chromaticity (Y) of the fourth color pixel within the above range. It is found that the difference between the chromaticity (x, y) of the fourth color pixel and the chromaticity (x, y) obtained by the additive color mixture of the red, green, and blue pixels can be reduced without limitation. It is characterized by having both white balance and high transmittance.

  Here, the pixel of the fourth color refers to a pixel that exhibits any one of red, green, and blue and has a pixel transmittance of 50% or more in the entire region having a wavelength of 400 to 700 nm.

  In the present invention, the pigment concentration in the total solid content in the fourth color pixel is required to be 0.3 to 3% by mass, and preferably 0.5 to 2% by mass. If the pigment concentration of the fourth color pixel is less than 0.3% by mass, the white balance of the color filter substrate becomes poor, and if the pigment concentration of the fourth color pixel is more than 3% by mass, the transmittance of the color filter substrate decreases. To do.

  Examples of the colorant used for the fourth color pixel include pigments and dyes. Examples of blue pigments include C.I. I. Pigment Blue (PB) 15, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, PB60 and the like. Examples of purple pigments include C.I. I. Pigment violet (PV) 19, PV23, PV37 and the like. Examples of red pigments include C.I. I. Pigment red (PR) 149, PR166, PR177, PR179, PR209, PR254, and the like.

  On the other hand, examples of blue dyes include C.I. I. Basic blue (BB) 5, BB7, BB9, BB26 and the like are listed. Examples of purple dyes include C.I. I. Basic violet (BV) 1, BV3, BV10, etc. are mentioned, and examples of red dyes include C.I. I. Acid Red (AR) 51, AR87, AR289, and the like.

Examples of the resin used for the fourth color pixel include acrylic, epoxy, and polyimide resins. A photosensitive acrylic resin is preferable because the manufacturing cost of the color filter substrate can be reduced. The acrylic resin generally contains at least an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator in order to impart photosensitivity.
Examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides.

  Examples of photopolymerizable monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol. Examples include penta (meth) acrylate.

  Examples of photopolymerization initiators include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone , Thioxanthone, 2-chlorothioxanthone and the like.

  Examples of photopolymerization initiators include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone , Thioxanthone, 2-chlorothioxanthone and the like.

  When a photosensitive acrylic resin is used as the resin in the present invention, an alkali-soluble resin, a photopolymerizable monomer, and a polymer dispersant added at the time of pigment dispersion are used as the resin component, and the total of the colorant and the resin component is completely added. Solid content.

  The chromaticity Y of the fourth color pixel needs to satisfy 70 ≦ Y ≦ 99, and preferably 75 ≦ Y ≦ 99. If Y is less than 70, the transmittance of the color filter substrate is reduced, and if Y is greater than 99, the white balance of the color filter substrate becomes poor.

  In the present invention, the chromaticity (Y) of the fourth pixel can be set to the above range by controlling the type and ratio of the pigment used for the fourth color pixel and the pigment concentration in the total solid content.

  The chromaticity (x, y) of the fourth color pixel in the present invention is preferably 0.250 ≦ x ≦ 0.350, and more preferably 0.275 ≦ x ≦ 0.320. The chromaticity y of the fourth color pixel is preferably 0.250 ≦ y ≦ 0.310, and more preferably 0.260 ≦ y ≦ 0.305. By setting the chromaticity (x, y) of the pixel of the fourth color in the above range, it is easy to achieve both white balance and high transmittance of the color filter substrate of the present invention.

  In the present invention, it is necessary to set the colorant concentration in the total solid content in the fourth color pixel to 0.3 to 3% by weight, which is extremely different from the colorant concentration of a general red, green, and blue pixel. Low. For this reason, it became clear by examination of the inventors that the pattern processing of a pixel becomes difficult because the colorant density | concentration which is excellent in alkali resistance is low. In order to improve pattern processing, in the present invention, the weight mixing ratio of the alkali-soluble resin and the photopolymerizable monomer in the fourth color pixel is preferably 55:45 to 15:85, and 50:50 to 20:80. More preferably. If the alkali-soluble resin is more than 55% by weight, the fourth color pixel chip may occur. On the other hand, if the alkali-soluble resin is less than 15% by weight, a residual may occur in the unexposed portion of the fourth color pixel.

  Further, in the present invention, it is necessary to set the colorant concentration in the total solid content in the fourth color pixel to 0.3 to 3% by weight, but at this concentration, a grain defect occurs in the fourth color pixel. It became clear by the inventors that it was easier. In order to suppress this grain defect, in the present invention, the photopolymerizable monomer A having a solid content acid value in the range of 0 to 50 mgKOH / g and a solid content acid value of 50 to 150 mgKOH / g in the fourth color pixel. It is preferable to use a photopolymerizable monomer B in the range of 1 and an alkali-soluble resin having a solid content acid value in the range of 50 to 150 mgKOH / g. That is, as a photopolymerizable monomer, the compatibility with an alkali-soluble resin can be improved by using a photopolymerizable monomer A having a low acid value and a photopolymerizable monomer B having a high acid value in combination. The grain defect can be suppressed even in the fourth color pixel having a low value.

  In the present invention, the weight mixing ratio of the alkali-soluble resin and the photopolymerizable monomer is 50:50 to 20:80, and the solid content acid value is in the range of 0 to 50 mgKOH / g, It is preferable to use a photopolymerizable monomer B having a solid content acid value in the range of 50 to 150 mgKOH / g and an alkali-soluble resin having a solid content acid value in the range of 50 to 150 mgKOH / g. As a result, it is possible to obtain a satisfactory fourth color pixel free from occurrence of pixel chipping, pixel grain, and residual.

  In the present invention, the red, green, and blue pixels need to contain a pigment, the red pixel contains PR254, the green pixel contains any pigment selected from PG7, PG36, and PG58, and blue It is necessary for the pixel to contain PB15: 6.

  The four-color filter substrate of the present invention has a triangular area formed by connecting the CIE1931 color system chromaticity (x, y) of red, green, and blue pixels measured using a C light source, and the NTSC standard chromaticity (x, The area of the triangle formed by connecting y) is preferably 65 to 100%, and more preferably 70 to 100%.

  The color filter substrate usually has a lower transmittance as the color reproduction range becomes wider. On the other hand, according to the study by the inventors, the color filter substrate has a relatively low transmittance of the green pixel among the red, green, and blue pixels in the color reproduction range of 65 to 100%. It was found that the additive color mixture chromaticity (x, y) of blue pixels tends to be blue to reddish chromaticity. On the other hand, the four-color filter substrate of the present invention allows the pigment concentration of the fourth color pixel to be in the above range and the chromaticity (Y) of the fourth color pixel to be in the above range. Since the difference between the chromaticity (x, y) of the four colors and the chromaticity (x, y) obtained by the additive color mixture of the red, green, and blue pixels can be reduced, even in the color reproduction range of 65 to 100%, It is easy to achieve both white balance and high transmittance.

  Examples of pigments other than PR254 used for the red pixel include PR149, PR166, PR177, PR209, PY138, PY150, and PYP139. Examples of pigments other than PG7, PG36, and PG58 used for the green pixel include PG37, PB16, PY129, PY138, PY139, PY150, and PY185. PV23 etc. are mentioned as an example of pigments other than PB15: 6 used for a blue pixel.

  In the present invention, the pigment concentration in the total solid content in the red pixel is preferably 20 to 50% by mass, the pigment concentration in the total solid content in the green pixel is preferably 30 to 50% by mass, It is preferable that the pigment density | concentration in the total solid in a blue pixel is 15-40 mass%.

  In the present invention, it is preferable that the film thicknesses of red, green, blue, and fourth color pixels are all in the range of 1.5 to 2.5 μm. Further, the difference in film thickness between the thickest pixel and the thinnest pixel is preferably in the range of 0 to 0.5 μm, and particularly preferably in the range of 0 to 0.2 μm. If the film thickness difference is larger than 0.5 μm, the flatness and adhesion of the color filter substrate tend to be lowered, and if the film thickness difference is larger than 0.2 μm, the contrast ratio of the color filter substrate tends to be lowered.

In the red, green, blue, and fourth color pixels, the area of the pixel having the smallest area is preferably 70 to 100% with respect to the area of the pixel having the largest area. If the area ratio is smaller than 70%, the color reproduction range tends to be narrow when the pixel with the smallest area is a red, green, and blue pixel, and the transmittance is low when the pixel with the smallest area is a pixel of the fourth color. Tend.
Next, a method for manufacturing the color filter substrate of the present invention will be described.

  The pigment used for the color filter substrate is nano-dispersed with a disperser together with a solvent, polymer dispersant, etc. to prepare a pigment dispersion, and then an alkali-soluble resin, monomer, photopolymerization initiator, etc. are added to the pigment dispersion. A pigment composition is prepared. On the other hand, when a dye is used as the colorant for the fourth color pixel, a solvent, an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like are added to the dye to prepare a colorant composition. A four-color filter substrate is obtained by patterning red, green, blue, and fourth color pixels on a transparent substrate using a pigment composition and a dye composition prepared for each color. Details will be described below.

  Since the pigment is in the form of secondary particles in which primary particles are aggregated in a powder state (secondary particles are usually 1 to 50 μm), the pigment is mixed with a solvent, a polymer dispersant, etc. It is necessary to apply a shear stress to the secondary particles of the pigment and disperse them into the particles of the primary particles or the aggregate of a small number of primary particles.

  Examples of solvents mixed with the pigment include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropionate, ethyl-3 -Ethoxypropionate, methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethanol, butanol, isopropanol, 3-methyl-3-methoxybutanol and the like.

  Examples of polymer dispersants to be mixed together with pigments are preferably those having a basic group in the structure. Examples of commercially available products are “Solsperse” (Abyssia), “Ajisper” (Ajinomoto Fine Techno) ), “BYK” (manufactured by Big Chemie) and the like can be preferably used. “Solsperse 24000,“ Ajisper ”PB821, PB822,“ BYK ”, 2000, 2001, 6919, 21116 and the like are preferable because the dispersion stabilization effect is increased.

  A sand mill, a ball mill, a bead mill, a three-roll mill, an attritor or the like is used as a disperser for applying a shear stress to coarse pigment particles in a solvent.

  A pigment composition is prepared by adding an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like to the pigment dispersion obtained as described above. In order to improve applicability, adhesion, and the like, a surfactant, an adhesion improver, and the like can be added.

  The pigment composition used in the present invention is preferably used in the range of 5 to 20% by mass of the total solid content of the pigment and the resin component, from the viewpoints of coating properties and drying properties.

  As a method of applying the pigment composition obtained as described above on a substrate, a method such as a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an ink jet printing method, a screen printing method or the like can be used. it can. As the substrate, a transparent substrate such as soda glass, alkali-free glass, borosilicate glass, or quartz glass is usually used. After the pigment composition is applied on the transparent substrate by the method as described above, a coating film of the pigment composition is formed by air drying, heat drying, vacuum drying or the like.

  Next, when the pigment composition is photosensitive, a mask is placed on the coating film of the photosensitive pigment composition, and exposure is selectively performed with ultraviolet rays using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp, or the like. Do.

  Thereafter, development is performed with an alkaline developer. Examples of the alkaline substance used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, n-propylamine, and the like. Examples include secondary amines such as tertiary amines, diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and organic alkalis such as tetramethylammonium hydroxide.

  Thereafter, the obtained coating film pattern is heat-treated to form a color filter substrate on which pixels are patterned. The heat treatment is usually performed in air, in a nitrogen atmosphere, in a vacuum, etc., and is performed continuously or stepwise at a temperature of 150 to 350 ° C., preferably 180 to 250 ° C., for 0.5 to 5 hours. Is called. By this heating step, curing of the resin component in the pigment composition proceeds.

  When the patterning process as described above is sequentially performed on red, green, blue, and fourth color pixels, the four-color filter substrate of the present invention can be manufactured. Examples of the pattern shape of each color pixel include a stripe type, a mosaic type, and a triangle type. The pixel patterning order is not limited.

  The color filter substrate of the present invention may be any of a transmissive type, a reflective type, and a transflective type, but is preferably a transmissive type because the manufacturing cost is low and the contrast ratio is high.

  For example, the white balance of the color filter substrate of the present invention is determined by measuring the chromaticity (x, y) of red, green, blue, and fourth color pixels in a C light source, and then measuring the chromaticity ( The absolute value (| Δx |, | Δy |) of the difference (Δx, Δy) between the chromaticity (x, y) obtained by the additive color mixture of the red, green, and blue pixels can be evaluated. The smaller the | Δx | and | Δy | are, the better the white balance of the color filter substrate is, and it is preferable that 0 ≦ | Δx | ≦ 0.005 and 0 ≦ | Δy | ≦ 0.005. preferable.

  In the present invention, the colorant concentration in the total solid content of the fourth color pixel is 0.3 to 3% by mass, and the chromaticity (Y) of the fourth color pixel is 70 ≦ Y ≦ 90. As a result, | Δx | and | Δy | can be in the above ranges.

  The transmittance of the color filter substrate of the present invention can be evaluated from the average of Y of red, green, blue, and fourth color pixels in a C light source, for example. Usually, as the color reproduction range increases, the transmittance of the color filter substrate decreases. Therefore, it is necessary to evaluate the transmittance with a constant color reproduction range.

  For example, the average of Y in a color reproduction range of 70% is preferably 30 or more, and more preferably 40 or more. By setting the colorant concentration in the total solid content of the fourth color pixel to 0.3 to 3% by mass and setting the chromaticity (Y) of the fourth color pixel to 70 ≦ Y ≦ 90, Y Can be within the above range.

  The color reproduction range of the color filter substrate of the present invention includes, for example, a triangular area formed by connecting the three chromaticities (x, y) of red, green, and blue pixels in a C light source and the NTSC standard chromaticity (x, y). ) Is calculated, and the area ratio can be calculated. The NTSC standard chromaticity (x, y) is red (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08).

  The color reproduction range of the color filter substrate of the present invention is preferably 65 to 100%, particularly preferably 70 to 100%. By appropriately selecting a combination of pigments used for red, green and blue pixels, the color reproduction range can be made 65 to 100%.

  The contrast ratio of the color filter substrate of the present invention is, for example, when the color filter substrate is placed between the polarizer and the analyzer, the transmittance when the polarizer and the analyzer are parallel, and when the polarizer and the analyzer are orthogonal to each other. It can be evaluated from the ratio to the transmittance. Usually, as the color reproduction range becomes larger, the contrast ratio of the color filter substrate decreases. Therefore, it is necessary to evaluate the contrast ratio with a constant color reproduction range. For example, the contrast ratio of the color filter substrate in a color reproduction range of 70% is preferably 6000 or more, and more preferably 7000 or more. In the present invention, the color filter substrate is formed by nano-dispersing and stabilizing pigments used for red, green, blue, and fourth color pixels, and reducing the film thickness difference between the red, green, blue, and fourth color pixels. The contrast ratio can be 6000 or more.

  Next, an example of a liquid crystal display device manufactured using this color filter substrate will be described. The color filter substrate and the array substrate are bonded to each other through a liquid crystal alignment film that has been subjected to a rubbing process for liquid crystal alignment provided on the substrate and a spacer for maintaining a cell gap. Note that a thin film transistor (TFT) element, a thin film diode (TFD) element, a scanning line, a signal line, and the like are provided over the array substrate, whereby a TFT liquid crystal display device and a TFD liquid crystal display device can be manufactured. Next, after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed. A liquid crystal display device is completed by attaching a backlight and mounting an IC driver or the like. As the backlight, a two-wavelength LED backlight, a three-wavelength LED backlight, a CCFL, or the like can be used, and a two-wavelength LED composed of a blue LED and a yellow YAG phosphor is used because the manufacturing cost of the liquid crystal display device is reduced. Is particularly preferred. The chromaticity (x, y) of the backlight used in the present invention is preferably 0.250 ≦ x ≦ 0.350 and 0.300 ≦ y ≦ 0.400. A display device comprising the backlight of the above chromaticity (x, y) and the color filter substrate of the present invention has good white display chromaticity (x, y) and is within the screen of the liquid crystal display device. The variation in white display chromaticity (x, y) at is small, and the white balance is excellent.

  Hereinafter, the present invention will be described in more detail using preferred embodiments. The color filter substrate in the examples was evaluated by the following method.

Evaluation method (chromaticity of pixels on the color filter substrate)
CIE1931 color system chromaticity (x, y, Y) of red, green, blue, and fourth color pixels in the C light source is measured using a microspectrophotometer “MCPD-2000” manufactured by Otsuka Electronics Co., Ltd. It was measured.

(Additive color mixture of red, green and blue pixels)
An additive color mixture of chromaticity (x, y, Y) of red, green, and blue pixels was performed, and an additive color mixture chromaticity (x, y, Y) was calculated.

(Transmission spectra of red, green, blue, and fourth color pixels)
Transmission spectra of red, green, blue, and fourth color pixels were measured using MCPD-2000 in the same manner as described above.

(Red, green, blue, and fourth color pixel film thickness)
The film thickness of the pixel was measured using a surface step meter “Surfcom 1400D” manufactured by Tokyo Seimitsu Co., Ltd.

(Fourth color pixel pattern processing)
The exposure time is adjusted to 100 and 200 mj / cm ² through a photomask having a line & space pattern of 10, 20, 30, 40, 50 μm on the substrate after the blue colorant composition is pre-baked. Adjusted and exposed to ultraviolet light.
Next, the exposed substrate was subjected to shower development for 60 seconds in a 0.2 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C., and then washed with pure water.

(Evaluation of the pixel color of the fourth color pixel)
About the board | substrate after pattern processing, the microscope observation of a 10-50 micrometers pattern was performed, and the following reference | standard determined.
○: Both the exposure dose 100 and 200 mj / cm ² have no chipping Δ: The exposure dose 100 or 200 mj / cm ² has blur ×: Both the exposure dose 100 and 200 mj / cm ² has blur (fourth color) Pixel grain evaluation of pixels
About the board | substrate after pattern processing, the microscope observation of a 10-50 micrometers pattern was performed, and the following reference | standard determined.
○: No grain in both exposure 100 and 200 mj / cm ² Δ: Grain in either exposure 100 or 200 mj / cm ² ×: Both in exposure 100 and 200 mj / cm ² (fourth color) Pixel residual evaluation)
About the board | substrate after pattern processing, the microscopic observation of the horizontal unexposed part of a 10 micrometers-50 micrometers pattern was performed, and the following reference | standard determined.
○: There is no residual in both the exposure dose 100 and 200 mj / cm ² Δ: There is a residual in either the exposure dose 100 or 200 mj / cm ² ×: Both the exposure dose 100 and 200 mj / cm ² have a residual ( (White balance of color filter substrate)
From the absolute value (| Δx |, | Δy |) of the difference (Δx, Δy) between the pixel chromaticity (x, y) of the fourth color and the additive color mixture chromaticity (x, y) of the red, green and blue pixels, the following The white balance of the color filter substrate was determined based on the standard.
Judgment ◎: When 0 ≦ | Δx | ≦ 0.005 and 0 ≦ | Δy | ≦ 0.005 Judgment ○: The larger of | Δx | and | Δy | is 0.005 <(| Δx | or | Δy |) ≦ 0.010 In the case of the determination Δ: | Δx |, | Δy | is larger when 0.010 <(| Δx | or | Δy |) ≦ 0.020 ×: | Δx |, | Δy | is larger than 0.020 <( | Δx | or | Δy |).

(Transmittance of color filter substrate)
The transmittance of the color filter substrate was calculated from the average Y of red, green, blue, and fourth color pixels.

(Contrast ratio of color filter substrate)
Light transmittance (I1) when the color filter substrate is placed between the polarizer and the analyzer so that the red, green, blue, and fourth color pixels fall within the total measurement area. The contrast ratio was calculated by measuring the ratio (I1 / I2) of the light transmittance (I2) when the polarizer and the analyzer were orthogonal. A polarizing film “NPF-G1220DUN” manufactured by Nitto Denko Corporation was used for the polarizer and the analyzer. “FL8A-EX / 70” manufactured by Meidaku System, which is a backlight unit using a hot cathode tube as a light source, was used, and “BM-5A” manufactured by Topcon Corporation was used as a color luminance meter.

(Color reproduction range of color filter substrate)
The area of the triangle formed by connecting the chromaticity coordinates (x, y) of the red, green, and blue pixels and the area of the triangle formed by connecting the NTSC standard chromaticity coordinates (x, y) are calculated. The color reproduction range of the color filter substrate was calculated from the ratio.

Adjustment example 1
(Preparation of a red pigment composition for forming a red pixel)
As pigments, 50 g of PR177 (manufactured by Dainichi Seika, “Chromofine” red, (trade name) 6125EC), 50 g of PR254 (manufactured by Ciba Specialty Chemicals, Inc., “Irgapore” red, (trade name) BK-CF ) Was mixed. In this pigment, 100 g of a polymer dispersant (manufactured by Big Me Japan Co., Ltd., (trade name) BYK2000, 40 mass% solution), 67 g of an alkali-soluble resin (manufactured by Daicel Chemical, “Cyclomer”, (trade name) ) ACA 250, 45 wt% solution), 83 g propylene glycol monomethyl ether, and 650 g propylene glycol monomethyl ether acetate were mixed to form a slurry. The beaker containing the slurry was connected with a circulation type bead mill disperser ("Dynomill" KDL-A manufactured by Willie et Bacofen) and a tube, and zirconia beads having a diameter of 0.3 mm were used as a medium at 3200 rpm for 4 hours. Dispersion treatment was performed to obtain a pigment dispersion.

  To 45.7 g of this pigment dispersion, 7.8 g of cyclomer ACA250, 3.3 g of photopolymerizable monomer (manufactured by Nippon Kayaku, “Kayarad”, (trade name) DPHA), 0.2 g of photopolymerization initiator (Ciba Specialty Chemicals, “Irgacure”, (trade name) 907), 0.1 g photopolymerization initiator (Nippon Kayaku, “Kaya Cure”, (trade name) DETX-S), 0.03 g interface An activator (BIC Chemie Japan Co., Ltd., (trade name) BYK333) and 42.9 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 31% by mass, and the mass mixing ratio of each pigment was PR177: PR254 = 50: 50.

Adjustment example 2
(Preparation of a red pigment composition for forming a red pixel)
To 36.8 g of the pigment dispersion obtained in Preparation Example 1, 10.0 g of Cyclomer ACA250, 3.7 g of Kayala DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333 and 49.2 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 25% by mass, and PR177: PR254 = 50: 50.

Adjustment example 3
(Preparation of a red pigment composition for forming a red pixel)
To 59.2 g of the pigment dispersion obtained in Preparation Example 1, 4.5 g of cyclomer ACA250, 2.5 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of By adding BYK333 and 33.5 g of propylene glycol monomethyl ether acetate, a pigment composition was obtained. The pigment concentration in the total solid content in the pigment composition was 40% by mass, and PR177: PR254 = 50: 50.

Adjustment example 4
(Preparation of a red pigment composition for forming a red pixel)
To 62.3 g of the pigment dispersion obtained in Preparation Example 1, 3.7 g of cyclomer ACA250, 2.4 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333 and 31.3 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 42% by mass, and PR177: PR254 = 50: 50.

Adjustment example 5
(Preparation of a green pigment composition for forming a green pixel)
As a pigment, 65 g of PG7 (“Hosta Palm” green, (trade name) GNX, manufactured by Clariant Japan Co., Ltd.) and 35 g of PY150 (manufactured by LANXESS, (trade name) E4GNGT) were mixed. In this pigment, 100 g of BYK2000, 67 g of cyclomer ACA250, 83 g of propylene glycol monomethyl ether, and 650 g of propylene glycol monomethyl ether acetate were mixed, and a zirconia bead having a diameter of 0.3 mm was used with Dinomill KDL-A. Was used for dispersion treatment at 3200 rpm for 6 hours to obtain a pigment dispersion.

  To 51.7 g of this pigment dispersion was added 6.3 g of Cyclomer ACA250, 2.9 g of Kayalad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, and 38.8 g. Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 35% by mass, and PG7: PY150 = 65: 35.

Adjustment example 6
(Preparation of a green pigment composition for forming a green pixel)
Pigment dispersion was performed in the same manner as in Preparation Example 5 except that 64 g of PG7, 34.5 g of E4GNGT, and 1.5 g of carbon black (Mitsubishi Chemical Corporation, (trade name) MA100) were mixed as the pigment. A liquid was obtained.

  To 51.7 g of this pigment dispersion was added 6.3 g of Cyclomer ACA250, 2.9 g of Kayalad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, and 38.8 g. Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 35% by mass, and PG7: PY150: carbon black = 64: 34.5: 1.5.

Adjustment example 7
(Preparation of a green pigment composition for forming a green pixel)
A pigment dispersion was obtained in the same manner as in Preparation Example 5, except that 75 g of PG36 (manufactured by DIC Corporation, “First Gen Green”, (trade name) 2YK-CF) and 25 g of E4GNGT were mixed as the pigment. It was.

  To 59.2 g of this pigment dispersion, 4.5 g of cyclomer ACA250, 2.5 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, and 33.5 g Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 40% by mass, and PG36: PY150 = 75: 25.

Adjustment example 8
(Preparation of a green pigment composition for forming a green pixel)
To 56.2 g of the pigment dispersion obtained in Preparation Example 5, 5.2 g of cyclomer ACA250, 2.7 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333 and 35.6 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition.
The pigment concentration in the total solid content in the pigment composition was 38% by mass, and PG7: PY150 = 65: 35.

Adjustment example 9
(Preparation of a green pigment composition for forming a green pixel)
As pigments, 10 g of PB16 (“Heliogen Blue” manufactured by BASF, (trade name) D7490), 40 g of PG58 (manufactured by DIC Corporation, “First Gen Green”, (trade name) A110), 25 g of PY129 ( A pigment dispersion was obtained in the same manner as in Preparation Example 5, except that “Irgazine Yellow” (trade name: 5GLT) manufactured by Ciba Specialty Chemicals Co., Ltd. and 25 g of PY150 were mixed.

  To 72.8 g of this pigment dispersion was added 1.1 g cyclomer ACA250, 1.8 g Kayarad DPHA, 0.2 g Irgacure 907, 0.1 g Kayacure DETX-S, 0.03 g BYK333, and 24 g propylene. Glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 49% by mass, and PB16: PG58: PY129: PY150 = 10: 40: 25: 25.

Adjustment example 10
(Preparation of blue pigment composition for forming blue pixel)
100 g of PB15: 6 (“Rionol” blue (trade name) 7602, manufactured by Toyo Ink Co., Ltd.) was used as a pigment, and 100 g of BYK2000, 67 g of cyclomer ACA250, 83 g of propylene glycol monomethyl ether, and 650 g were used as the pigment. A propylene glycol monomethyl ether acetate was mixed to prepare a slurry. The slurry was subjected to a dispersion treatment at 3200 rpm for 3 hours using a zirconia bead having a diameter of 0.3 mm using a disperser DYNOMILL KDL-A to obtain a pigment dispersion.

  To 41.3 g of this pigment dispersion was added 8.9 g of Cyclomer ACA250, 3.5 g of Kayalad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, and 46 g of propylene. Glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 28% by mass, and PB15: 6 alone.

Adjustment example 11
(Preparation of blue pigment composition for forming blue pixel)
A pigment dispersion was obtained in the same manner as in Preparation Example 10, except that 98 g of PB15: 6 and 2 g of MA100 were mixed as the pigment.

  To 41.3 g of this pigment dispersion was added 8.9 g of Cyclomer ACA250, 3.5 g of Kayalad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, and 46 g of propylene. Glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 28% by mass, and PB15: 6: carbon black = 98: 2.

Adjustment example 12
(Preparation of blue pigment composition for forming blue pixel)
To 24.9 g of the pigment dispersion obtained in Preparation Example 10, 13 g of cyclomer ACA250, 4.4 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, And 57.4 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 17% by mass, and PB15: 6 alone.

Adjustment example 13
(Preparation of blue pigment composition for forming blue pixel)
A pigment dispersion was obtained in the same manner as in Preparation Example 10, except that 80 g of PB15: 6 and 20 g of PV23 (“Costa Palm” violet, (trade name) RL-COF02, manufactured by Clariant Japan) were mixed as the pigment. It was.

  To 29.4 g of this pigment dispersion was added 11.9 g Cyclomer ACA250, 4.2 g Kayarad DPHA, 0.2 g Irgacure 907, 0.1 g Kayacure DETX-S, 0.03 g BYK333, and 54.2 g. Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 20% by mass, and PB15: 6: PV23 = 80: 20.

Adjustment example 14
(Preparation of blue pigment composition for forming blue pixel)
To 24.9 g of the pigment dispersion obtained in Preparation Example 13, 13 g of cyclomer ACA250, 4.4 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, And 57.4 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 17% by mass, and PB15: 6: PV23 = 80: 20.

Adjustment example 15
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.00 g of the pigment dispersion obtained in Preparation Example 10, 8.30 g of cyclomer ACA250 (alkali-soluble resin), 5.65 g of Kayarad DPHA (photopolymerizable monomer A), 0.20 g of Irgacure 907, 0 .10 g Kayacure DETX-S, 0.03 g BYK333, and 84.72 g propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6 alone.

  The solid content acid value of ACA250 was 70 mgKOH / g, the solid content acid value of DPHA was 0.1 mgKOH / g, and the weight mixing ratio of the resin and the monomer was ACA250: DPHA = 40: 60.

Adjustment example 16
(Preparation of composition for forming fourth color pixel)
Add 8.30 g Cyclomer ACA250, 5.65 g Kayarad DPHA, 0.2 g Irgacure 907, 0.1 g Kayacure DETX-S, 0.03 g BYK333, and 84.72 g propylene glycol monomethyl ether acetate A composition was obtained. This composition contained no pigment.

Adjustment example 17
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 0.50 g of the pigment dispersion obtained in Preparation Example 10, 8.40 g of cyclomer ACA250, 5.69 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333 and 85.08 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 0.5% by mass, and PB15: 6 alone.

Adjustment example 18
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.98 g of the pigment dispersion obtained in Preparation Example 10, 8.12 g of the cyclomer ACA250, 5.57 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333 and 84.00 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 2% by mass, and PB15: 6 alone.

Adjustment example 19
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 3.96 g of the pigment dispersion obtained in Preparation Example 10, 7.74 g of cyclomer ACA250, 5.40 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333 and 82.57 g of propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 4% by mass, and PB15: 6 alone.

Adjustment example 20
(Preparation of a light-color pigment composition for forming a fourth color pixel)
As a pigment, 50 g of PB15: 6 and 50 g of PG7 were mixed. 100 g of BYK2000, 67 g of cyclomer ACA250, 83 g of propylene glycol monomethyl ether, and 650 g of propylene glycol monomethyl ether acetate were mixed in this pigment to prepare a slurry. The slurry was subjected to a dispersion treatment at 3200 rpm for 3 hours using a zirconia bead having a diameter of 0.3 mm using a disperser DYNOMILL KDL-A to obtain a pigment dispersion.

  To 1.00 g of this pigment dispersion, 8.30 g of Cyclomer ACA250, 5.65 g of Kayarad DPHA, 0.20 g of Irgacure 907, 0.10 g of Kayacure DETX-S, 0.03 g of BYK333, and 84.72 g Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6: PG7 = 50: 50.

Adjustment example 21
(Preparation of a light-color pigment composition for forming a fourth color pixel)
As a pigment, 50 g of PB15: 6 and 50 g of PV23 were mixed. 100 g of BYK2000, 67 g of cyclomer ACA250, 83 g of propylene glycol monomethyl ether, and 650 g of propylene glycol monomethyl ether acetate were mixed in this pigment to prepare a slurry. The slurry was subjected to a dispersion treatment at 3200 rpm for 3 hours using a zirconia bead having a diameter of 0.3 mm using a disperser DYNOMILL KDL-A to obtain a pigment dispersion.
To 0.50 g of this pigment dispersion, 8.40 g of Cyclomer ACA250, 5.69 g of Kayarad DPHA, 0.2 g of Irgacure 907, 0.1 g of Kayacure DETX-S, 0.03 g of BYK333, and 85.08 g Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 0.5% by mass, and PB15: 6: PV23 = 50: 50.

Adjustment example 22
(Preparation of a light-color pigment composition for forming a fourth color pixel)
Using 100 g of PV23 as a pigment, 100 g of BYK2000, 67 g of cyclomer ACA250, 83 g of propylene glycol monomethyl ether, and 650 g of propylene glycol monomethyl ether acetate were mixed in this pigment to prepare a slurry. The slurry was subjected to a dispersion treatment at 3200 rpm for 2 hours using a zirconia bead having a diameter of 0.3 mm using a disperser DYNOMILL KDL-A to obtain a pigment dispersion.

  To 1.00 g of this pigment dispersion, 8.30 g of Cyclomer ACA250, 5.65 g of Kayarad DPHA, 0.20 g of Irgacure 907, 0.10 g of Kayacure DETX-S, 0.03 g of BYK333, and 84.72 g Of propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass and was PV23 alone.

Adjustment example 23
(Preparation of a light-color pigment composition for forming a fourth color pixel)
A light color pigment composition was prepared in the same manner as in Preparation Example 15 except that 100 g of PB15: 3 (manufactured by Clariant Japan, “Hosta Palm” blue, (trade name) B2G)) was used as the pigment.

  The pigment concentration in the total solid content in the pigment composition was 1% by mass, and the pigment ratio was PB15: 3 alone.

Reference Example 24
A light color pigment composition was prepared in the same manner as in Preparation Example 15 except that 100 g of PB60 (manufactured by Clariant Japan, “Hosta Palm” blue, (trade name) RL01) was used as the pigment.

  The pigment concentration in the total solid content in the pigment composition was 1.5% by mass, and the pigment ratio was PB60 alone.

Reference Example 25
A light color pigment composition was prepared in the same manner as in Preparation Example 15 except that 70 g of PB15: 6, 30 g of PV19 (manufactured by Clariant Japan, “Hosta Palm” Red Violet, (trade name) ER02) was used as the pigment. did.

  The pigment concentration in the total solid content in the pigment composition was 2.5% by mass, and the pigment ratio was PB15: 6: PV19 = 70: 30.

Reference Example 26
A light color pigment composition was prepared in the same manner as in Preparation Example 15 except that 30 g of PV23 and 70 g of PR177 were used as the pigment.

  The pigment concentration in the total solid content in the pigment composition was 2% by mass, and the pigment ratio was PV23: PR177 = 30: 70.

Reference Example 27
A light-color pigment composition was prepared in the same manner as in Preparation Example 15 except that 30 g of PV23 and 70 g of PR209 (manufactured by Clariant Japan, “Hosta Palm” red, (trade name) EGtransp.) Were used as the pigment.

  The pigment concentration in the total solid content in the pigment composition was 2% by mass, and the pigment ratio was PV23: PR209 = 30: 70.

Reference Example 28
A light color pigment composition was prepared in the same manner as in Preparation Example 15 except that 50 g of PV23 and 50 g of PR254 were used as the pigment.

  The pigment concentration in the total solid content in the pigment composition was 1.5% by mass, and the pigment ratio was PV23: PR254 = 50: 50.

Reference Example 29
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.00 g of the pigment dispersion obtained in Preparation Example 10, 4.19 g of cyclomer ACA250 (alkali-soluble resin), 7.66 g of Kayarad DPHA (photopolymerizable monomer A), 0.20 g of Irgacure 907, 0 .10 g Kayacure DETX-S, 0.03 g BYK333, and 86.82 g propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6 alone.

  The solid content acid value of ACA250 was 70 mgKOH / g, the solid content acid value of DPHA was 0.1 mgKOH / g, and the weight mixing ratio of the resin and the monomer was ACA250: DPHA = 20: 80.

Reference Example 30
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.00 g of the pigment dispersion obtained in Preparation Example 10, 2.06 g of cyclomer ACA250 (alkali-soluble resin), 8.62 g of Kayarad DPHA (photopolymerizable monomer A), 0.20 g of Irgacure 907, 0 .10 g Kayacure DETX-S, 0.03 g BYK333, and 87.99 g propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6 alone.

  The solid content acid value of ACA250 was 70 mgKOH / g, the solid content acid value of DPHA was 0.1 mgKOH / g, and the weight mixing ratio of resin and monomer was ACA250: DPHA = 10: 90.

Reference Example 31
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.00 g of the pigment dispersion obtained in Preparation Example 10, 10.57 g of cyclomer ACA250 (alkali-soluble resin), 4.79 g of Kayarad DPHA (photopolymerizable monomer A), 0.20 g of Irgacure 907, 0 .10 g Kayacure DETX-S, 0.03 g BYK333, and 83.31 g propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6 alone.

  The solid content acid value of ACA250 was 70 mgKOH / g, the solid content acid value of DPHA was 0.1 mgKOH / g, and the weight mixing ratio of the resin and the monomer was ACA250: DPHA = 50: 50.

Reference Example 32
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.00 g of the pigment dispersion obtained in Preparation Example 10, 12.70 g of cyclomer ACA250 (alkali-soluble resin), 3.83 g of Kayarad DPHA (photopolymerizable monomer A), 0.20 g of Irgacure 907, 0 .10 g Kayacure DETX-S, 0.03 g BYK333, and 82.14 g propylene glycol monomethyl ether acetate were added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6 alone.

  The solid content acid value of ACA250 was 70 mgKOH / g, the solid content acid value of DPHA was 0.1 mgKOH / g, and the weight mixing ratio of the resin and the monomer was ACA250: DPHA = 60: 40.

Reference Example 33
(Preparation of a light-color pigment composition for forming a fourth color pixel)
To 1.00 g of the pigment dispersion obtained in Preparation Example 10, 8.30 g of cyclomer ACA250 (alkali-soluble resin), 4.71 g of Kayarad DPHA (photopolymerizable monomer A), 0.94 g of photopolymerizable monomer B (manufactured by Toa Gosei, “Aronix”, (trade name) M510, photopolymerizable monomer B), 0.20 g Irgacure 907, 0.10 g Kayacure DETX-S, 0.03 g BYK333, and 84.72 g Propylene glycol monomethyl ether acetate was added to obtain a pigment composition. The pigment concentration in the total solid content in the pigment composition was 1% by mass, and PB15: 6 alone.

  The solid content acid value of ACA250 was 70 mgKOH / g, the solid content acid value of DPHA was 0.1 mgKOH / g, and the solid content acid value of M510 was 93 mgKOH / g. The weight mixing ratio of the resin and the monomer was ACA250: DPHA: M510 = 40: 50: 10.

Example 1
(Fabrication of 4-color filter substrate with red, green, blue and fourth color pixels)
A red colored film was obtained by applying the red pigment composition obtained in Preparation Example 1 on a glass substrate on which a black matrix was prepared, using a spinner, and then heat-treating at 90 ° C. for 10 minutes in a hot air oven. Next, after exposing a predetermined area through a negative mask, 0.04% aqueous potassium hydroxide solution was used as a nonionic surfactant “Emulgen” A-60 (HLB12.8, polyoxyethylene derivative)) (Kao Corporation) Was developed by immersing in an alkaline developer added with 0.1% by mass of the developer for 90 seconds with shaking for 90 seconds, and then washed with pure water to obtain a patterned substrate. The obtained patterned substrate was held in a hot air oven at 220 ° C. for 30 minutes to cure the acrylic resin. A red pixel was formed as described above. Next, in the same manner as for the red pixel, the green pigment composition of Preparation Example 5, the blue pigment composition of Preparation Example 10 and the light color pigment composition of Preparation Example 15 were used. Colored pixels were produced. Thereafter, a transparent electrode was formed to obtain a four-color filter substrate having red, green, blue, and fourth color pixels. In addition, the spinner rotation speed of each composition was adjusted so that each film thickness after hardening of a red, green, and blue light-colored pixel might be 2.0 micrometers.

Examples 2-6, Comparative Examples 1-4
Examples 2 to 6 and Comparative Example 1 were the same as Example 1 except that the pigment composition and the pixel film thickness for producing red, green, blue, and fourth color pixels were changed. 4 color filter substrates of ˜4 were prepared. Table 1 shows the pigment compositions used.

However, Comparative Example 1 was a color filter substrate on which pixels of the fourth color were not formed, and each film thickness of red, green, and blue pixels was 2.0 μm.
In Examples 2 to 5 and Comparative Examples 2 to 4, the film thicknesses of the red, green, blue, and fourth color pixels were set to 2.0 μm. In Example 6, the thickness of each of the red, green, blue, and fourth color pixels was 2.5 μm.

Table 2 shows evaluation results of chromaticity (x, y, Y) of red, green, blue, and fourth color pixels.

Table 3 shows various evaluation results of the color filter substrate.

  As shown in Tables 1 to 3, since Comparative Example 1 did not form the fourth color pixel, the transmittance of the color filter substrate was low and the result was poor. In Example 1, since the pigment concentration of the pixel of the fourth color is 1% by mass and Y = 88.2 of the pixel of the fourth color, the four-color color filter substrate has an excellent white balance and a high The transmittance was good and the result was good.

  Examples 1 to 3 and Comparative Examples 2 and 3 are the results of changing the pigment density of the fourth color pixel. In Examples 1 to 3, since the pigment concentration of the fourth color pixel is 0.3 to 3% by mass and the Y of the fourth color pixel is 70 ≦ Y ≦ 99, the color filter substrate is The white balance was excellent (judgment ◎ or ◯) and the transmittance was high. On the other hand, in Comparative Example 2, since the pixels of the fourth color did not contain the pigment, the color filter substrate had poor white balance (determination x).

  In Comparative Example 3, since the pigment concentration of the fourth color pixel was 4% by mass, the color filter substrate had poor white balance (judgment x) and low transmittance.

  In Comparative Example 4, the fourth color pixel is the same as in Comparative Example 2, and the improvement of the white balance of the four-color filter substrate is studied by limiting the chromaticity of the red, green, and blue pixels. Compared with Comparative Example 2, the color filter substrate of Comparative Example 4 showed a poor result although the white balance was slightly improved (Decision Δ). When comparing the color filter substrate of Example 1 in which the chromaticity of the red, green, and blue pixels is not limited to that of Comparative Example 4 in which the chromaticity of the red, green, and blue pixels is limited, Example 1 is more white balance, transmittance, and contrast. The ratios were all good. The color reproduction ranges of Examples 1 to 3 and Comparative Examples 1 to 4 were the same at 70%.

  In Examples 1, 4 to 6, the color reproduction range was changed in the range of 60 to 100%. The color filter substrates of Examples 1 and 4 to 6 were excellent in white balance (judgment ま た は or ◯), high transmittance, and high contrast ratio.

  Further, as shown in Tables 2 and 3, the additive color mixture chromaticity (x, y) of red and blue green pixels tended to increase as y and the y decreased as the color reproduction range increased. In Examples 1 and 4 to 6, in the color reproduction range of 60 to 100%, the chromaticity (x, y) of the pixel of the fourth color is controlled by the type of pigment, the pigment concentration, and the film thickness. The difference from the additive color mixture chromaticity (x, y) of the pixel can be reduced, and both the white balance and the high transmittance of the color filter substrate of the fourth color pixel can be achieved.

  1 to 3 show transmission spectra of red, green, blue, and fourth color pixels of the color filter substrates of Example 1, Comparative Example 2, and Example 6. FIG.

  The fourth color pixel was light blue in FIG. 1, white in FIG. 2, and light purple in FIG. On the other hand, in any of FIGS. 1 to 3, the spectrum area of the green pixel is smaller than the spectrum area of the blue pixel and the red pixel in the red-green-blue pixel spectrum.

Example 7
(Production of liquid crystal display device)
An array substrate was produced by forming TFT elements, transparent electrodes, etc. on alkali-free glass. A polyimide alignment film was formed on this array substrate and the color filter substrate obtained in Example 1, and a rubbing treatment was performed. Next, a sealant kneaded with microrods was printed on the array substrate, and a bead spacer having a thickness of 6 μm was sprayed, and then the array substrate and the color filter substrate were bonded together. After injecting nematic liquid crystal (“Rixon” JC-5007LA made by Chisso) from the injection port provided in the seal part, a polarizing film was laminated on both surfaces of the liquid crystal cell so that the polarization axes were perpendicular to obtain a liquid crystal panel. A two-wavelength backlight composed of a blue LED and a yellow phosphor was attached to this liquid crystal panel. The chromaticity (x, y) of this two-wavelength backlight was (0.324, 0.330). Furthermore, a TAB module, a printed circuit board, and the like were mounted to manufacture a liquid crystal display device.

  When this liquid crystal display device performed white display, it was uniform without unevenness. When the white display chromaticity (x, y) of this liquid crystal display device was measured at 10 points, it was 0.300 ≦ x ≦ 0.305 and 0.305 ≦ y0.310, and white display in the screen of the liquid crystal display device The chromaticity variation was small and the result was good.

Comparative Example 5
(Production of liquid crystal display device)
A liquid crystal display device was produced in the same manner as in Example 7 except that the color filter substrate obtained in Comparative Example 2 was used.

  When this liquid crystal display device performed white display, it was uneven and non-uniform. When the white display chromaticity (x, y) of this liquid crystal display device was measured at 10 points, it was 0.300 ≦ x ≦ 0.324 and 0.305 ≦ y0.326, and the white display in the screen of the liquid crystal display device The variation in chromaticity was large and the result was poor.

Examples 8-13
The four-color colors of Examples 8 to 13 are the same as in Example 1 except that the pigment composition and the pixel film thickness for producing red, green, blue, and fourth color pixels are changed. A filter substrate was produced. Table 4 shows the pixel configuration.

  In Examples 8 to 10, the red, green, blue, and fourth color pixels have a thickness of 2.0 μm, and in Examples 11 to 13, the red, green, blue, and fourth color pixels. Each film thickness was set to 2.5 μm.

Table 5 shows evaluation results of chromaticity (x, y, Y) of red, green, blue, and fourth color pixels.

Table 6 shows various evaluation results of the color filter substrate.

  In Examples 8 to 10, the color reproduction range is set to 70%, and the pigment type and pigment density of the fourth color pixel are changed. The color filter substrates of Examples 6 to 8 all had good white balance, transmittance, and contrast ratio.

In Examples 11 to 13, the color reproduction range is set to 100%, and the pigment type and pigment density of the fourth color pixel are changed. The color filter substrates of Examples 11 to 13 all had good white balance, transmittance, and contrast ratio.

Examples 14-18
The four-color color filters of Examples 14 to 18 were the same as Example 1 except that the alkali-soluble resin and the photopolymerizable monomer in the pigment composition for producing the fourth color pixel were changed. A substrate was produced. Table 7 shows the composition of the fourth color pixel, and Table 8 shows various evaluation results of the fourth color pixel and the color filter substrate.

  Examples 1 and 14 to 17 are the results of changing the ratio of the alkali-soluble resin and the photopolymerizable monomer. In Examples 1, 14, and 16, since the ratio of the alkali-soluble resin and the photopolymerizable monomer was in the range of 50:50 to 20:80, good results were obtained for both the pixel chip and the residual.

  In Example 15, since the weight mixing ratio of alkali-soluble resin: photopolymerizable monomer was 10:90, the residual was poor. In Example 17, the weight mixing ratio of alkali-soluble resin: photopolymerizable monomer was 60: Since it was 40, the pixel chip was defective. Also, in Example 1 and Examples 14 to 17, the pixel grains were all defective.

  Example 18 uses an alkali-soluble resin having an acid value of 70 mgKOH / g, a photopolymerizable monomer A having an acid value of 0.1 mgKOH / g, and a photopolymerizable monomer B having an acid value of 93 mgKOH / g. : Monomer A: Monomer B = 40: 50: 10. For the fourth color pixel of Example 18, good results were obtained for pixel chip, pixel grain, and residual, and the contrast ratio of the color filter substrate was 9000.

  The color filter substrate of the present invention can be suitably used for a liquid crystal display or the like.

Claims (6)

In a four-color filter substrate having a red pixel, a green pixel, a blue pixel, and a fourth color pixel, the red pixel is a C.I. I. Pigment Red 254 and green pixels are C.I. I. Pigment green 7, C.I. I. Pigment green 36, or C.I. I. Pigment Green 58 is contained, and the blue pixel is C.I. I. Pigment Blue 15: 6, the fourth color pixel contains a colorant and a resin, and the colorant concentration in the total solid content of the fourth color pixel is 0.3 to 3% by mass. And the CIE1931 color system chromaticity (Y) of the pixel of the fourth color measured using the C light source is
70 ≦ Y ≦ 99
A color filter substrate characterized by the above. The fourth color pixel contains a pigment as a colorant, and the pigment is C.I. I. Pigment Blue (PB) 15, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16, PB60, C.I. I. Pigment violet (PV) 19, PV23, PV37, C.I. I. 2. The color filter substrate according to claim 1, wherein the color filter substrate is one or more selected from pigment red (PR) 149, PR166, PR177, PR179, PR209, and PR254. The fourth color pixel contains an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator as a resin, and the weight mixing ratio of the alkali-soluble resin and the photopolymerizable monomer is 50:50 to 20:80. The color filter substrate according to claim 1, wherein the color filter substrate is a color filter substrate. The photopolymerizable monomer is composed of a polymerizable monomer A having a solid content acid value in the range of 0 to 50 mgKOH / g and a polymerizable monomer B having a solid content acid value in the range of 50 to 150 mgKOH / g, 4. The color filter substrate according to claim 3, wherein the solid content acid value of the alkali-soluble resin is in the range of 50 to 150 mgKOH / g. The area of a triangle connecting the CIE 1931 color system chromaticity (x, y) of the red, green, and blue pixels measured using a C light source connects NTSC standard chromaticity (x, y) 3 The color filter substrate according to claim 1, wherein the color filter substrate is 65 to 100% of a square area. A liquid crystal display device comprising the color filter substrate according to any one of claims 1 to 5.

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