JP4368158B2 - Photosensitive coloring composition, color filter, and liquid crystal panel - Google Patents

Description

  The present invention relates to a photosensitive resin composition for a color filter, a color filter using the same, and a liquid crystal panel.

  The liquid crystal panel has a structure in which a display side substrate and a liquid crystal driving side substrate are opposed to each other, and a liquid crystal compound is sealed between them to form a thin liquid crystal layer. A liquid crystal display device incorporating such a liquid crystal panel selectively changes the amount of transmitted or reflected light of the display side substrate by electrically controlling the liquid crystal alignment in the liquid crystal layer by the liquid crystal drive side substrate of the liquid crystal panel. Display.

  There are various drive systems such as static drive system, simple matrix system, and active matrix system, but in recent years, liquid crystal panels of active matrix system or simple matrix system have been used as flat displays for personal computers and personal digital assistants. The used color liquid crystal display devices are rapidly spreading. Each driving method has several driving modes. For example, in the case of the active matrix method, there are driving modes such as TN, IPS, and VA, and the layer configuration of the color filter changes depending on the driving mode.

  FIG. 1 is a configuration example of an active matrix type liquid crystal panel. The liquid crystal panel 101 is provided with a gap portion 3 of about 1 to 10 μm so that the color filter 1 as a display side substrate and the TFT array substrate 2 as a liquid crystal drive side substrate face each other, and the liquid crystal L is filled in the gap portion 3. The periphery is sealed with a sealing material 4. The color filter 1 includes a black matrix layer 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually red (R (R)) to form each pixel. ), Green (G), blue (B) three primary colors) are arranged in a predetermined order, or recently a pixel part using a hologram is stacked in this order from the side close to the transparent substrate. ing. In the TN mode, the transparent electrode film 9 is provided on the pixel portion 7 or the protective film 8. In the IPS mode, the protective film 8 is provided on the pixel portion, and the transparent electrode film 9 may be formed on the opposite surface of the transparent substrate 5 from the pixel portion 7. In the IPS mode, the black matrix layer must be a resin black matrix. In the VA mode, a transparent electrode is formed on the pixel portion 7 or the protective film 8, and the transparent electrode may be patterned. In particular, in the MVA mode, a projection called protolution is formed on the transparent electrode 9.

  On the other hand, the TFT array substrate 2 has a structure in which TFT elements are arranged on a transparent substrate and a transparent electrode film is provided (not shown). An alignment film 10 is provided on the inner surface side of the color filter 1 and the TFT array substrate 2 facing the color filter 1. A color image is obtained by controlling the light transmittance of the liquid crystal layer behind the pixels colored in the respective colors.

  As a method of maintaining the cell gap, as shown in FIG. 1, a large number of spherical or rod-like particle spacers 11 of a certain size made of glass, alumina, plastic, or the like are scattered in the gap 3 as a spacer. A method of injecting liquid crystal by laminating with the TFT array substrate 2, or as shown in FIG. 2, in the cell gap in a region overlapping the position where the black matrix layer 6 is formed on the inner surface side of the color filter. There is a method of forming a columnar spacer 12 having a corresponding height.

  In a liquid crystal display device incorporating a color filter having the above structure, a color image is obtained by controlling the light transmittance of the liquid crystal layer behind each pixel that is colored in each color and arranged in a predetermined pattern.

  Liquid crystal display devices (LCDs) have the advantage of energy saving and space saving, so they are attracting attention as displays that replace conventional CRT monitors, and are rapidly spreading as monitors for OA devices and personal computers.

  With the spread of the Internet and mobile phones, not only text information but also images and images are distributed, so that images can be exchanged through media such as personal computer monitors, printers, digital cameras, and scanners. A common standard for color space and color reproduction that conforms to A typical example of the standardization of the hue image signal transmission method is sRGB (international standard IEC 61966-2-1).

The color gamut of the multimedia monitor is determined by the chromaticity of the three primary colors of the receiver (the three primary colors of the receiver). The three primary colors of the liquid crystal monitor of the sRGB standard are determined as follows for the chromaticity coordinates x and y in the XYZ color system.
Red: x = 0.64; y = 0.33
Green: x = 0.30; y = 0.60
Blue: x = 0.15; y = 0.06

  In recent years, the spread of liquid crystal color televisions is accelerating due to the drop in prices of liquid crystal panels. However, at present, it is very difficult to provide a liquid crystal color television with display performance comparable to that of a CRT.

  In color television, through the processes of (1) imaging (color camera), (2) transmission, and (3) image receiving (receiver), the shape, movement, and hue of the subject are reproduced on the image screen, and the image including the hue is also included. The signal transmission method is standardized. Typical examples of this system are NTSC (National Television System Committee) and EBU (European Broadcasting Union). NTSC is adopted as a standard and standard for television broadcasting in Japan, the United States, Canada, etc., and EBU is adopted in Europe.

The color reproduction range of a color television is determined by the chromaticity of the three primary colors of the receiver (the three primary colors of the receiver), and the spectral characteristics that the color camera should have are determined by this. The NTSC standard image receiving three primary colors are defined as follows for chromaticity coordinates x and y in the XYZ color system.
Red: x = 0.67; y = 0.33
Green: x = 0.21; y = 0.71
Blue: x = 0.14; y = 0.08

On the other hand, the image receiving three primary colors of the EBU standard are defined as follows.
Red: x = 0.64; y = 0.33
Green: x = 0.29; y = 0.60
Blue: x = 0.15; y = 0.06
Note that x = X / (X + Y + Z), y = Y / (X + Y + Z), and X, Y, and Z are tristimulus values in the XYZ color system.

  However, in order for a color television to exhibit excellent display performance, it is necessary that the color reproduction range satisfies the above-mentioned standard and the screen is bright, and the luminance is required to be sufficiently high. In a CRT phosphor, if the color gamut is too wide, the luminance is extremely reduced. Therefore, in the current CRT color television, the color reproduction range is sacrificed in order to ensure the necessary luminance, and it is suppressed to about 75% as compared with the NTSC standard displayable space.

  In order for a liquid crystal color television to have a display performance similar to that of a CRT, it is also required that the color reproduction range satisfies the color television display standard and that the luminance is sufficient. In order to realize a wide color reproduction range and high luminance, a combination of the spectral characteristics of the light source and the color reproduction ability of the color filter is important.

  The light source spectrum has different emission line positions for each backlight manufacturer, but has a peak at about 545 nm, and sub-emission lines exist at wavelengths around that. For this reason, a pigment having a high transmittance at 545 nm and its surroundings is required for a high transmission color filter. A high color purity color filter requires a pigment having a narrow half-value width that has a transmittance only in the main bright line. For this reason, color filters also have two development factors and demands for high luminance and high color gamut.

  Regarding the green pixel of the color filter, in order to ensure a wide color gamut while maintaining high luminance, it is required to be able to color green with a strong yellowish color. Among the standards, the sRGB standard for multimedia monitors requires green pixels that are particularly yellowish, and the NTSC and EBU standards that are compatible with televisions also require green pixels that are strong yellow, but they are blue compared to the sRGB standards. The taste is green. However, no matter which display standard is adopted, it is very difficult to form green pixels that are close to the three primary colors and have high brightness to a level that can ensure a sufficient color gamut with only one type of green pigment. is there. Therefore, in order to ensure sufficient luminance in a sufficient color reproduction range, the transmittance of the secondary emission line is kept low, and the transmittance is high mainly for green pigments having a high transmittance around 545 nm, which is the green wavelength. It is desirable to form a highly transparent pixel with high coloring power while sufficiently coloring by using a combination of yellow pigments and suppressing the total amount of pigment used.

  In the green pixel of the color filter, C.I. mainly composed of a chlorinated copper phthalocyanine pigment has been conventionally used as a green pigment. I. Pigment Green 7 (hereinafter referred to as PG7) and a brominated copper phthalocyanine pigment. I. Pigment Green 36 (hereinafter referred to as PG36) is used. PG7 has a high coloring power as green, but is too bluish, and it is necessary to mix a large amount of yellow in order to obtain a green pixel of sRGB, NTSC, EBU standards, and the transmittance is low. When a green pixel is formed around the center, it becomes a dark color filter. On the other hand, PG36 shows a spectral transmittance spectrum that is relatively yellowish, and has a wide half-value width and a wide spectral transmittance width near the peak top. As shown, coloring power is low. Therefore, if an attempt is made to form a green pixel that displays an area with high coloring power on the color coordinates (high density area), the amount of pigment used by PG 36 increases and the luminance decreases. In order to ensure high luminance, there is a method of shifting the color coordinate in the yellow direction by increasing the concentration of the yellow pigment. However, since the amount of yellow pigment used increases, the total amount of pigment used increases. Accordingly, there has been a demand for pigments that replace conventional copper halide phthalocyanine pigments such as PG7 and PG36.

  In general, when the proportion of the green pigment in the photosensitive coloring composition (photosensitive coloring resist) increases, the transparency of the pixel decreases and it is difficult to increase the luminance. Further, when the pigment blending ratio in the photosensitive color composition for forming a color filter increases, the blending ratio of the dispersing agent also increases, and the blending ratio of components relating to film forming properties such as a binder and a developing component becomes relatively small. . When the binder and the developing component are reduced, there is a problem that the fine pattern forming ability and physical properties of the pixel are adversely affected. Moreover, when using the pigment with low coloring power, if the pigment compounding ratio in the photosensitive coloring composition is suppressed, it is necessary to increase the film thickness for coloring. Even when the film thickness increases, there is a problem in that the fine pattern forming ability and physical properties of the pixel are adversely affected.

  For example, in the case of producing a fine pattern of pixels by a so-called pigment dispersion method, there is no residue, no foreign matter remains, high resolution, accurate shape after development, film formation, Performance such as uniform thickness is required.

  The residue is a colored product remaining in a portion that should not remain after development, and is likely to occur when developability is poor due to a large amount of pigments or dispersants. The foreign matter is generated due to, for example, a part of a pixel being missing when there are few curing components in the photosensitive coloring composition, or a colored piece produced by peeling development with few developing components. In order to improve resolution, the liquid crystal drive system has evolved, and the color filter has a pattern with many curved parts and corners, unlike the conventional stripe pattern. There is a need to.

  There is a problem that the shape after development becomes an inverted trapezoid (reverse tapered shape) when the photosensitive coloring composition has poor photosensitivity. If the post-development shape becomes an inverted trapezoid, the upper part of the pixel tends to be chipped due to water pressure during development, which causes the above-mentioned foreign matter. Further, when the reverse trapezoidal film has low heat resistance, a portion protruding in a comb shape may hang down due to heat and form a hole after post-baking. This hole not only degrades the display quality but also reduces the resolution. In addition, the liquid crystal is contaminated when heated and burst in the liquid crystal panel assembly.

  Film thickness uniformity is not a major problem at the individual pixel level. However, for the purpose of cost reduction, the substrate size has been steadily increasing and has been applied to the metric class. In that case, if the film thickness is different between the glass center and the edge, the color varies, resulting in a defective product.

In addition, regarding the physical properties of the completed pixel, performance such as hardness, elasticity, and impurity elution is required.
In order to form a high color purity liquid crystal display device, it is desirable to selectively provide columnar spacers in the opening region without using spherical spacers that degrade display quality. However, even if a columnar spacer having a high hardness is formed, if the hardness and elastic modulus of the pixel and the black matrix are inferior, the uniformity of the cell gap is impaired due to the deformation of the base.

  For this reason, even a pixel is required to have high hardness and elastic modulus. However, if the blending ratio of the pigment and the dispersant in the photosensitive coloring composition is increased and the amount of the binder is decreased accordingly, the pixel cannot have sufficient hardness and elastic modulus.

  Impurity elution from the pixel causes liquid crystal contamination. Since the liquid crystal does not perform the switching function only by mixing a small amount of conductive impurities, it is important that the conductive molecules do not dissolve into the liquid crystal layer from the color filter. However, conductive pigments are often included as impurities in pigments and dispersants used for pixels. Therefore, it is important to suppress the elution of impurities by increasing the cross-linking density of the film and capturing molecules with a dense network.

  On the other hand, Patent Document 1 discloses a color filter containing at least one phthalocyanine pigment whose central metal is VO, Al-Z, or In-Z (Z represents a halogen atom, a hydroxyl group, an alkoxy group, or an aryloxy group). A composition for use is described. In Patent Document 2, C.I. I. Pigment green 7 and / or C.I. I. In the color filter composition containing CI Pigment Green 36, C.I. I. Pigment green 7 and C.I. I. A color filter composition containing a phthalocyanine pigment having a maximum transmittance wavelength longer than that of CI Pigment Green 36 is described. I. Pigment green 7 and / or C.I. I. It is used by mixing with Pigment Green 36.

  Patent documents 3 to 5 are disclosed after the earliest priority date of the present application. Patent Document 3 discloses at least one halogenated copper phthalocyanine pigment and a central metal selected from the group consisting of Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge, and Sn. Disclosed is a color filter coloring composition comprising a green colorant comprising a different metal phthalocyanine pigment, and wherein the content of the halogenated different metal phthalocyanine pigment is 1 to 80 mol% based on the total amount of the green colorant. However, the halogenated dissimilar metal phthalocyanine pigment is also used by mixing with halogenated copper phthalocyanine.

  Patent Document 4 discloses a color filter containing one or more phthalocyanine compounds selected from the group consisting of a pigment, a phthalocyanine compound having no central metal, and a phthalocyanine compound having a central metal other than copper. Although a composition is described, it is described that a relatively small amount of the phthalocyanine compound is used.

  In Patent Document 5, the green pixel portion includes (1) a halogenated metal phthalocyanine pigment in which 8 to 16 halogen atoms per phthalocyanine molecule are bonded to the benzene ring of the phthalocyanine molecule, and (2) visible light. A color filter characterized by exhibiting a maximum transmittance at 520 to 590 nm in the spectral transmission spectrum over the entire region is described.

  However, a photosensitive coloring composition that sufficiently satisfies the purpose of forming a color filter having a wide color reproduction range and high brightness has not been known yet.

JP 2002-131521 A JP 2002-162515 A JP 2002-250812 A JP 2003-161821 A JP 2003-161827 A

  The present invention has been accomplished in view of such circumstances, and a first object thereof is to provide a photosensitive coloring composition capable of forming a color filter having a wide color reproduction range and high luminance. .

  In addition, the second object of the present invention is to provide a photosensitive coloring composition that has a high proportion of reactive components, is close to each standard green pixel with a relatively small amount of pigment, and is excellent in plate making. is there.

  A third object of the present invention is to provide a photosensitive coloring composition capable of forming a green pixel having a sufficiently strong yellowishness and green color even if the amount of yellow pigment is small.

  In addition, a fourth object of the present invention is to provide a color filter having a wide color reproduction range and high brightness, in which a green pixel is formed using the photosensitive coloring composition, and a liquid crystal panel using the color filter. There is.

The photosensitive coloring composition according to the present invention comprises at least a reactive component involved in the curing reaction, a brominated zinc phthalocyanine containing an average of less than 13 bromine in one molecule as a first green pigment, and F10 alone From a green pigment for a color filter capable of displaying an xy chromaticity coordinate region (hereinafter, also referred to as “region A”) surrounded by the following equations 1, 2 and 3 in the CIE XYZ color system when colorimetric with a light source As a second green pigment, it consists of brominated zinc phthalocyanine containing 13 or more bromine on average in one molecule, and in the XYZ color system of CIE when measured alone with F10 light source One kind selected from green pigments for color filters that can display the xy chromaticity coordinate region (hereinafter, also referred to as “region C”) surrounded by equations 4, 5 and 6 is small. It contains a coloring component comprising also.

(Equation 1)
y = 2.640 × x + 0.080
However, in Equation 1, 0.180 <x <0.230
(Equation 2)
y = 5261.500 × x ⁴ −6338.700 × x ³ + 2870.400 × x ² −580.730 × x + 44.810
However, in Equation 2, 0.230 <x <0.350
(Equation 3)
y = −36.379 × x ³ + 37.410 × x ² −13.062 × x + 1.907
However, in Equation 3, 0.180 <x <0.350
(Equation 4)
y = 8.000 × x−1.513
However, in Equation 4, 0.260 <x <0.270
(Equation 5)
y = −1051.300 × x ⁴ + 1176.900 × x ³ −450.880 × x ² + 62.131 × x−0.836
However, in Equation 5, 0.260 <x <0.350
(Equation 6)
y = 5746.700 × x ⁴ −7310.300 × x ³ + 3493.200 × x ² −744.610 × x + 60.251
However, in Equation 6, 0.270 <x <0.350

  The first green pigment can display the xy chromaticity coordinate region surrounded by the above equations 1, 2, and 3 in the CIE XYZ color system when the green pigment alone is coated. In the chromaticity coordinate area that could not be displayed with the halogenated copper phthalocyanine green pigment, it developed a green color with excellent tinting strength, not too strong bluish color and high transmittance, and expanded the color reproduction area compared with the conventional green pigment. be able to.

  The second green pigment can display the xy chromaticity coordinate region surrounded by the equations 4, 5 and 6 in the XYZ color system of CIE when forming a coating film with the green pigment alone. It produces a green color with high coloring power and high transmittance. The second green pigment is capable of developing a green color with a strong yellow tint in the chromaticity coordinate region that could not be displayed with a conventional copper halide phthalocyanine pigment. The color reproduction range can be expanded, and the amount of yellow pigment for toning can be reduced. Furthermore, since the second green pigment has a higher coloring power than PG36, it can be close to the standard green color with a smaller amount than when PG36 is used.

Therefore, when the first green pigment and the second green pigment are appropriately selected and used in combination, it is possible to bring the color of a green pixel close to that of each standard with a small amount of pigment used. In the case of forming pixels, the film thickness can be reduced, the platemaking property is improved, and a fine shape can be easily formed by photolithography. In addition, even if the amount of the yellow pigment is small, it is possible to form a green pixel having a sufficiently strong yellowish green color and / or a thin and highly transparent color pixel. The color gamut can be expanded with a thinner film thickness than when using pigments.
In the first green pigment and the second green pigment, since the central metal is the same, the compatibility is good, that is, the same dispersant system can be obtained, so that dispersion stability is improved when mixed. .
Since the first green pigment and the second green pigment are brominated zinc phthalocyanine, the dispersion stability of the pigment is good and the transmittance is high.

  In addition, since both the first and second green pigments have high transmittance, when a green pixel is formed in combination with a yellow pigment, it is conventional even in a region where the coloring power of color coordinates is high (high density region). The brightness can be increased with a thinner film thickness. Therefore, when a color filter is formed using the photosensitive coloring composition according to the present invention, a color filter having a wide color reproduction range and a high luminance can be formed. Compared to the case of forming with a conventional photosensitive coloring composition using a halogenated copper phthalocyanine pigment, the light transmittance of the color filter is increased, so that a strong backlight is not necessary, and the cost and consumption of the liquid crystal panel are increased. An increase in power can be suppressed.

  The first green pigment has a wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum, and is 500 to 520 nm, and the second green pigment has a spectral transmittance spectrum at 380 to 780 nm. It is preferable that the wavelength (Tmax) that maximizes the transmittance of 520 to 535 nm.

  When the brominated zinc phthalocyanine green pigment having an average primary particle size of 0.01 to 0.1 μm is used as the first and second green pigments, dispersibility in a colored resin or the like is particularly good, and coloring It is preferable from the point that power increases more.

  The mass ratio (b / a) of the non-reactive component (b) other than the colored component to the reactive component (a) is preferably 0.45 or less from the viewpoint of improving the plate-making property. That is, the photosensitive coloring composition can provide sufficient color developability with a small amount of pigment, so the amount of the pigment and the dispersant used for dispersing the pigment is reduced, and the amount of the reactive component is relatively increased. be able to. Therefore, the photocurability is good, and a green pixel having excellent physical properties such as hardness, elasticity, film thickness uniformity, suppression of chipping, residue reduction, developability improvement, crosslink density improvement, thinning, and the like is obtained.

  The above-mentioned photosensitive coloring composition can produce a color that can sufficiently cope with a high concentration type even with a very small amount of pigment as a high concentration type photosensitive coloring composition having a pigment / vehicle ratio of 0.25 to 1.0. A green pixel with high density and high transparency can be formed.

  Moreover, in order to form a green pixel, the said photosensitive coloring composition can be made to contain at least 1 or more yellow pigment with said 1st and 2nd green pigment. In this case, sufficient color developability can be obtained even under conditions with a small amount of yellow pigment such that the mass ratio of the yellow pigment to the green pigment containing the first and second green pigments (yellow pigment / green pigment) is 1.6 or less. Therefore, the amount of yellow pigment used can also be reduced.

The color filter which concerns on this invention is provided with a green pixel using the photosensitive coloring composition of the said invention.
When the green pixel has a film thickness of 2.5 μm or less and is measured with a single pixel by an F10 light source, the x coordinate is 0.25 ≦ x ≦ 0.32 and the y coordinate is 0 in the CIE XYZ color system. A color space in which .55 ≦ y ≦ 0.75 and the stimulus value Y is in the range of 30 ≦ Y can be displayed. Therefore, a wide color reproduction region can be secured by combining with pixels of other colors, and the luminance is very high even if the film thickness is thin.

  In addition, the green pixel can be strengthened in yellow just by mixing a small amount of yellow pigment, and the mass ratio of the yellow pigment to the green pigment containing the first and second green pigments in the pixel (yellow pigment) / Green pigment) is 1.6 or less, the x coordinate is 0.25 ≦ x ≦ 0.32 and the y coordinate is 0.55 in the CIE XYZ color system when color measurement is performed with a F10 light source with a single pixel. An xy chromaticity coordinate region in a range of ≦ y ≦ 0.75 can be displayed.

In addition, since the green pixel has a high crosslinking density, it has a hardness of 500 N / mm ² or more or an elastic deformation rate of 20% or more and is not easily deformed.

  Further, the green pixel does not have a reverse taper shape when developing, and is formed in a taper shape in which the ratio of the upper base length to the lower base length of the pixel cross section (upper base / lower base) is less than 1. The pattern shape is good.

  The liquid crystal panel according to the present invention is obtained by enclosing the color filter of the present invention and a liquid crystal driving side substrate and enclosing liquid crystal therebetween. By using the color filter and the liquid crystal panel of the present invention, it becomes possible to manufacture a liquid crystal display device that can satisfy the display standards of multimedia monitors such as sRGB or the color TV display standards such as NTSC and EBU.

  In the photosensitive coloring composition according to the present invention, the first green pigment and the second green pigment are appropriately selected and used in combination, so that the color of the green pixel specified in each standard is approximated with a small amount of pigment used. As a result, it is possible to reduce the film thickness when forming the pixel of the color filter, so that the plate-making property is improved and a fine shape can be easily formed by photolithography. In addition, even if the amount of the yellow pigment is small, it is possible to form a green pixel having a sufficiently strong yellowish green color and / or a thin and highly transparent color pixel. The color gamut can be expanded with a thinner film thickness than when pigments are used. In addition, since both the first and second green pigments have high transmittance, when a green pixel is formed in combination with a yellow pigment, it is conventional even in a region where the coloring power of color coordinates is high (high density region). The brightness can be increased with a thinner film thickness. Therefore, when a color filter is formed using the photosensitive coloring composition according to the present invention, a color filter having a wide color reproduction range and a high luminance can be formed. Compared to the case of forming with a conventional photosensitive coloring composition using a halogenated copper phthalocyanine pigment, the light transmittance of the color filter is increased, so that a strong backlight is not necessary, and the cost and consumption of the liquid crystal panel are increased. An increase in power can be suppressed.

  Furthermore, in the photosensitive coloring composition according to the present invention, the blending ratio of the green pigment and the yellow pigment to be used is reduced, and as a result, the amount of the dispersant used is also reduced. As a result, the photosensitive component involved in the photocuring reaction is reduced. The blending ratio increases, and a green pixel excellent in various physical properties such as hardness, elasticity, shape, and film thickness uniformity can be obtained.

  Since the green pixel formed using such a photosensitive coloring composition according to the present invention has a wide color reproduction region, high brightness, and excellent physical properties, the green pixel is provided. Using color filters and liquid crystal panels with high display performance, areas with high coloring power (high density areas) such as display standards for multimedia monitors such as sRGB or display standards such as NTSC and EBU A satisfactory liquid crystal display device can be manufactured.

  The present invention is described in detail below. In the present invention, (meth) acryl means either an acrylic group or a methacryl group, and (meth) acryloyl means either an acryloyl group or a methacryloyl group. The light includes electromagnetic waves and radiation having wavelengths in the visible and non-visible regions, and the radiation includes, for example, microwaves and electron beams, and specifically refers to electromagnetic waves and electron beams having a wavelength of 5 μm or less. .

  The photosensitive coloring composition according to the present invention comprises at least a reactive component involved in a curing reaction, a phthalocyanine green pigment as a first green pigment, and a CIE XYZ color system when measured alone with an F10 light source. 1 type selected from green pigments for color filters capable of displaying an xy chromaticity coordinate region (hereinafter, also referred to as “region A”) surrounded by the following equations 1, 2 and 3 as the second green pigment An xy chromaticity coordinate region (hereinafter, also referred to as “region C”) that is composed of phthalocyanine green pigment and is surrounded by the following equations 4, 5 and 6 in the CIE XYZ color system when measured by a single F10 light source. The coloring component which contains at least 1 type selected from the green pigment for color filters which can display is contained. FIG. 3 shows the xy chromaticity coordinate region (region A) surrounded by the equations 1, 2, and 3 and the xy chromaticity coordinate region (region C) surrounded by the equations 4, 5, and 6.

(Equation 1)
y = 2.640 × x + 0.080
However, in Equation 1, 0.180 <x <0.230
(Equation 2)
y = 5261.500 × x ⁴ −6338.700 × x ³ + 2870.400 × x ² −580.730 × x + 44.810
However, in Equation 2, 0.230 <x <0.350
(Equation 3)
y = −36.379 × x ³ + 37.410 × x ² −13.062 × x + 1.907
However, in Equation 3, 0.180 <x <0.350
(Equation 4)
y = 8.000 × x−1.513
However, in Equation 4, 0.260 <x <0.270
(Equation 5)
y = −1051.300 × x ⁴ + 1176.900 × x ³ −450.880 × x ² + 62.131 × x−0.836
However, in Equation 5, 0.260 <x <0.350
(Equation 6)
y = 5746.700 × x ⁴ −7310.300 × x ³ + 3493.200 × x ² −744.610 × x + 60.251
However, in Equation 6, 0.270 <x <0.350

  The above equation is a display in the CIE XYZ color system when colorimetry is performed with an F10 light source. The F10 light source is a light source defined in JIS Z 8719 (1984) and is similar to the light source of a television backlight. Has a spectroscopic spectrum. Color measurement can be performed using a microspectrophotometer (for example, OSP-SP200 microspectrophotometer manufactured by Olympus Corporation).

  In addition, in order to measure the color of the first or second green pigment by itself, a coating liquid is prepared by blending the green pigment with an appropriate dispersant, binder component and solvent, and transparent. What is necessary is just to apply | coat and dry on a board | substrate and to make it harden | cure as needed. As a binder component, a non-curable thermoplastic resin composition may be used as long as a transparent coating film capable of performing colorimetry can be formed, or a photo-curable (photosensitive) or thermosetting resin composition. May be used. Further, by using a composition obtained by removing other pigments from the photosensitive coloring composition of the present invention, a coating film containing only the first or second green pigment is formed as the pigment, and colorimetry is performed. You can also.

  Among the coloring components in the photosensitive coloring composition of the present invention, the phthalocyanine green pigment used as the first green pigment has a wavelength at which the transmittance of the spectral transmittance spectrum is minimized from the point that the region A can be displayed ( When Tmin) is 5%, the wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum is preferably 500 to 520 nm. Further, the transmittance at the wavelength (Tmax) is preferably 90% or more, particularly 93% or more. The phthalocyanine green pigment used as the first green pigment preferably has a transmittance of the spectral transmittance spectrum at 435 nm, which is the wavelength of the blue light source of the F10 light source, of 45% or less, particularly 40% or less. The transmittance of the spectral transmittance spectrum at 610 nm which is the wavelength of the red light source of the F10 light source is preferably 20% or less, particularly preferably 10% or less. In addition, the spectral transmittance spectrum in the present invention can be measured using a microspectrophotometer (for example, OSP-SP200 microspectrophotometer manufactured by Olympus Corporation).

  Further, the phthalocyanine green pigment used as the second green pigment in the coloring component of the photosensitive coloring composition of the present invention has the minimum transmittance of the spectral transmittance spectrum from the point that the region C can be displayed. When the wavelength (Tmin) is 5%, the wavelength (Tmax) that maximizes the transmittance of the spectral transmittance spectrum at 380 to 780 nm is preferably 520 to 535 nm. Further, the transmittance at the wavelength (Tmax) is preferably 90% or more, particularly 93% or more. The phthalocyanine green pigment used in the present invention preferably has a transmittance of the spectral transmittance spectrum at 435 nm, which is the wavelength of the blue light source of the F10 light source, of 40% or less, particularly 35% or less. The transmittance of the spectral transmittance spectrum at 490 nm which is the sub wavelength of the three-wavelength tube is preferably 85% or less, particularly preferably 80% or less. Furthermore, the transmittance of the spectral transmittance spectrum at 610 nm, which is the wavelength of the red light source of the F10 light source, is preferably 30% or less, particularly preferably 25% or less.

  Examples of the central metal of the phthalocyanine green pigment used as the first and second green pigments according to the present invention include Zn, Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Ge, and Sn. It is done. In the first green pigment and the second green pigment, the central metal of the phthalocyanine green pigment may be different, but the central metal is the same, the compatibility is good, that is, the same dispersing agent system Therefore, it is preferably used in the present invention from the viewpoint that the dispersion stability becomes good when mixed and the color development becomes good. In particular, in the first green pigment and the second green pigment, when the central metal of the phthalocyanine green pigment is Zn (zinc), the coloring power and transmittance are high, and the xy chromaticity coordinate region in the above range. Is preferable because it can be displayed. Zinc is very suitable for displaying the sRGB standard for multimedia monitors, or its surrounding chromaticity region, and the NTSC, EBU standard green for television.

Since zinc phthalocyanine has 16 hydrogen atoms in one molecule, when these hydrogen atoms are substituted with bromine atoms and chlorine atoms, the number of bromine atoms is 0 to 16, and the number of chlorine atoms is 0 to 16 In theory, a total of 136 kinds of substitution products can be produced in the range of 0 to 16 hydrogen atoms. Among them, the green pigment made of brominated zinc phthalocyanine, in which at least one hydrogen atom is substituted with a bromine atom, can display the region A and the region C, the first green pigment, It is preferably used as the second green pigment.
As the first green pigment, brominated zinc phthalocyanine having an average of 8 or more and less than 13 bromine atoms in one molecule is a green color that has good coloring power as green, is not too bluish, and has high transmittance. Is preferable because it is very suitable for forming a green pixel of a color filter. Among these, brominated zinc phthalocyanine having an average of 10 to 11 bromine atoms in one molecule is preferable.

  As the second green pigment, brominated zinc phthalocyanine having an average of 13 or more bromine atoms in one molecule develops a green color with high tinting power and high transmissivity while having a strong yellow tint. This is preferable because it is very suitable for forming a green pixel. Of these, brominated zinc phthalocyanine having an average of 13 to 16 bromine atoms in one molecule and not containing chlorine or having an average of 3 or less in one molecule is preferable. Brominated zinc phthalocyanine having 14 to 16 and not containing chlorine in one molecule or having an average of 2 or less is preferable.

  Such a brominated zinc phthalocyanine pigment can be produced by a known production method disclosed in JP-A-50-130816. For example, a method of synthesizing a pigment using phthalic acid or phthalodinitrile in which some or all of the hydrogen atoms of the aromatic ring are substituted with a halogen atom such as chlorine in addition to bromine as an appropriate starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may be used as necessary.

  As another method, a method of brominating zinc phthalocyanine with bromine gas in a melt of about 110 to 170 ° C. composed of a mixture of aluminum chloride, sodium chloride, sodium bromide and the like can be mentioned. In this method, the ratio of various brominated zinc phthalocyanines with different bromine contents can be adjusted by adjusting the ratio of chloride and bromide in the molten salt, or by changing the amount of chlorine gas introduced and the reaction time. Can be controlled arbitrarily.

  When the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid after the reaction is completed, the produced brominated zinc phthalocyanine is precipitated. Thereafter, post-treatment such as filtration, washing and drying is performed to obtain brominated zinc phthalocyanine.

  The brominated zinc phthalocyanine pigment is dry-ground in a grinder such as an attritor, ball mill, vibration mill, vibration ball mill, etc., if necessary, and then pigmented by a solvent salt milling method or a solvent boiling method. Thus, a brominated zinc phthalocyanine pigment that is excellent in dispersibility and coloring power and develops a light green color is obtained. There is no particular limitation on the pigmentation method, and the bromination zinc phthalocyanine may be dispersed in the dispersion medium and at the same time the pigmentation may be performed, but rather than the solvent treatment in which the brominated zinc phthalocyanine is heated and stirred in a large amount of organic solvent, It is preferable to employ a solvent salt milling treatment in that pigment particles that can easily suppress crystal growth and have a large specific surface area can be obtained.

  The solvent salt milling means kneading and grinding brominated zinc phthalocyanine, a crude pigment immediately after synthesis, an inorganic salt, and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve it are charged into a kneader, and kneading and grinding are performed therein. As a kneader at this time, for example, a kneader, a mix muller, or the like can be used.

  As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.

  In obtaining a brominated zinc phthalocyanine pigment having an average primary particle size of 0.01 to 0.1 μm, it is preferable to increase the amount of inorganic salt used relative to the amount of crude pigment used in solvent salt milling. That is, the amount of the inorganic salt used is preferably 5 to 20 parts by mass, more preferably 7 to 15 parts by mass with respect to 1 part by mass of the crude pigment. In addition, the average particle diameter of the primary particles in the present invention refers to the primary pigments constituting aggregates on a two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.). For 50 particles, the longer diameter (major diameter) is obtained and averaged. At this time, the pigment as a sample is ultrasonically dispersed in a solvent and then photographed with a microscope. A scanning electron microscope may be used instead of the transmission electron microscope.

  As the organic solvent, it is preferable to use an organic solvent capable of suppressing crystal growth, and as such an organic solvent, a water-soluble organic solvent can be suitably used. For example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene Glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene group Call, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, can be used dipropylene glycol. Although the usage-amount of the said water-soluble organic solvent is not specifically limited, 0.01-5 mass parts is preferable with respect to 1 mass part of crude pigments.

  In the method for producing a brominated zinc phthalocyanine pigment, only the crude pigment may be subjected to solvent salt milling, but it is also possible to perform solvent salt milling using a brominated zinc phthalocyanine and a phthalocyanine derivative in combination. The phthalocyanine derivative may be added at the time of synthesizing the crude pigment or after pigmentation, but is more preferably added before the pigmentation step such as solvent salt milling. By adding the phthalocyanine derivative, it is possible to improve the viscosity characteristics and the dispersion stability of the color filter resist ink.

As such a phthalocyanine derivative, any known and commonly used phthalocyanine derivatives can be used, but phthalocyanine pigment derivatives of the following general formula (I) or (II) are preferred.
Formula (I): P- (Y) _m
General formula (II): P- (AZ) _n
(In the formula, P represents a residue obtained by removing n hydrogens of an unsubstituted or halogenated phthalocyanine ring having no central metal or having a central metal. Y represents a primary to tertiary amino group or a carboxylic acid group. Represents a sulfonic acid group or a salt thereof with a base or a metal, A is a divalent linking group, Z is a residue obtained by removing at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or (Represents a residue obtained by removing at least one hydrogen on a nitrogen atom of a heterocyclic ring containing nitrogen, and m represents 1-4, and n represents 1-4).

Examples of the central metal include divalent to trivalent metals such as copper, zinc, cobalt, manganese, and aluminum. Examples of the primary and secondary amino groups include a monomethylamino group, a dimethylamino group, and a diethylamino group. Is mentioned. Examples of the base or metal that forms a salt with the carboxylic acid group or sulfonic acid group include ammonia, organic bases such as dimethylamine, diethylamine, and triethylamine, and metals such as potassium, sodium, calcium, strontium, and aluminum. As the divalent linking group for A, for example, a divalent linking group such as an alkylene group having 1 to 3 carbon atoms, —CO ₂ —, —SO ₂ —, —SO ₂ NH (CH ₂ ) _m —, etc. Groups. Examples of Z include a phthalimide group, a monoalkylamino group, and a dialkylamino group.

  The added phthalocyanine derivative is usually 0.01 to 0.3 parts by mass per 1 part by mass of the crude pigment. When a phthalocyanine derivative is used, the total amount of the crude pigment and the phthalocyanine derivative is regarded as the amount of the crude pigment used, and the amount of the inorganic salt used is selected from the above range.

  30-150 degreeC is preferable and the temperature at the time of solvent salt milling has more preferable 80-120 degreeC. The solvent salt milling time is preferably 5 to 20 hours, more preferably 6 to 18 hours.

  By this solvent salt milling, a mixture containing a brominated zinc phthalocyanine pigment, an inorganic salt and an organic solvent as main components is obtained. The organic solvent and the inorganic salt are removed from this mixture, and if necessary, the brominated zinc phthalocyanine pigment is mainly used. By washing, filtering, drying, pulverizing, and the like, a brominated zinc phthalocyanine pigment powder can be obtained. As washing, either water washing or hot water washing can be employed. The number of washings can be repeated in the range of 1 to 5 times. In the case of the mixture using a water-soluble inorganic salt and a water-soluble organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water.

  Examples of the drying after filtration and washing described above include batch-type or continuous drying in which the pigment is dehydrated and / or desolvated by heating at 80 to 120 ° C. with a heating source installed in a dryer. Examples of the dryer generally include a box dryer, a band dryer, and a spray dryer. In addition, the pulverization after drying is not an operation for increasing the specific surface area or reducing the average particle diameter of the primary particles, but for example, the pigment is a lamp as in the case of drying using a box dryer or a band dryer. When it becomes a shape or the like, it is performed to break the pigment into powder, and examples thereof include mortar, hammer mill, disk mill, pin mill, jet mill and the like.

  Thus, a brominated zinc phthalocyanine pigment having an average primary particle size of 0.01 to 0.1 μm is obtained. In particular, a pigment having an average primary particle diameter of 0.01 to 0.1 μm has better dispersibility in a synthetic resin to be colored. In addition, the brominated zinc phthalocyanine pigment has a property that the primary particles have a weaker cohesive force than conventional pigments, and are more easily unraveled. From the electron micrograph, it is possible to observe individual pigment primary particles constituting the aggregate, which cannot be observed with a conventional pigment.

  In addition, in the case where the first and second green pigments are used in a color filter, the average particle diameter of primary particles of the brominated zinc phthalocyanine pigment is in the range of 0.01 to 0.1 μm. Is relatively weak, makes it easy to disperse the pigment in the color filter coloring composition, and more easily obtains a color filter having both high definition and brightness. Also, when curing the color filter coloring composition, The light shielding property at 365 nm, which is frequently used for the film, is reduced, the photocuring sensitivity of the resist is not lowered, and film edge and pattern flow during development are less likely to occur.

  Further, the first and second green pigments have a primary particle having an aspect ratio of 1 to 3 with improved viscosity characteristics and higher fluidity in each application field. In order to obtain the aspect ratio, first, as in the case of obtaining the average particle diameter of the primary particles, the pigment particles in the field of view are photographed with a transmission electron microscope or a scanning electron microscope. Then, an average value of the longer diameter (major axis) and the shorter diameter (minor axis) of 50 primary pigment particles constituting the aggregate on the two-dimensional image is obtained and calculated using these values. To do.

  The first green pigment obtained as described above can display the region A when the green pigment alone is formed into a coating film, and the chromaticity which cannot be displayed with the conventional copper halide phthalocyanine green pigment. In the coordinate area, the color is excellent in coloring power and the blue color is not too strong and the transmittance is high, and the color reproduction area can be expanded as compared with the case of using a conventional green pigment.

  In addition, the second green pigment can display the region C when forming a coating film with the green pigment alone, and develops a green color with high coloring power and high transmittance while being yellowish. To do. The second green pigment is capable of developing a green color with a strong yellow tint in the chromaticity coordinate region that could not be displayed with a conventional copper halide phthalocyanine pigment. The color reproduction range can be expanded, and the amount of yellow pigment for toning can be reduced. Furthermore, since the second green pigment has a higher coloring power than PG36, it can be close to the standard green color with a smaller amount than when PG36 is used.

  Therefore, when the first green pigment and the second green pigment are appropriately selected and used in combination, it is possible to bring the color of a green pixel close to that of each standard with a small amount of pigment used. In the case of forming pixels, the film thickness can be reduced, the platemaking property is improved, and a fine shape can be easily formed by photolithography. In addition, even if the amount of the yellow pigment is small, it is possible to form a green pixel having a sufficiently strong yellowish green color and / or a thin and highly transparent color pixel. The color gamut can be expanded with a thinner film thickness than when pigments are used.

  In addition, since both the first and second green pigments have high transmittance, when a green pixel is formed in combination with a yellow pigment, it is conventional even in a region where the coloring power of color coordinates is high (high density region). The brightness can be increased with a thinner film thickness. Therefore, when a color filter is formed using the photosensitive coloring composition according to the present invention, a color filter having a wide color reproduction range and a high luminance can be formed. Compared to the case of forming with a conventional photosensitive coloring composition using a halogenated copper phthalocyanine pigment, the light transmittance of the color filter is increased, so that a strong backlight is not necessary, and the cost and consumption of the liquid crystal panel are increased. An increase in power can be suppressed.

  In the coloring component of the present invention, the first green pigment is selected from green pigments for color filters that can display the region A as described above, and the second green pigment is a color filter that can display the region C as described above. The green pigment is selected from the above-mentioned green pigments. Further, when the distance between the first green pigment and the second green pigment is fixed at y = 0.50 on the xy chromaticity coordinate region, x is 0.02 or more, It is preferably 0.02 to 0.05 away from the point that it has a high effect of bringing the color reproduction range close to the color of each standard green pixel with a relatively small amount of pigment used and widening the color reproduction range.

As the first green pigment, the xy chromaticity coordinate region (hereinafter referred to as “region B”) surrounded by the following equations 7, 8, and 9 in the CIE XYZ color system when the color is measured with an F10 light source alone. It is preferable that it is a green pigment capable of displaying “)” because the blue color is not too strong and the luminance is not lowered, and the yellow color is not too strong and the coloring power as green is not reduced. . An xy chromaticity coordinate region (region B) surrounded by the following equations 7, 8 and 9 is shown in FIG. 4 together with the regions A and C.
(Equation 7)
y = 4.000 × x−0.270
However, in Equation 7, 0.210 <x <0.220
(Equation 8)
y = 3849.200 × x ⁴ −4595.600 × x ³ + 2056.300 × x ² −409.710 × x + 31.138
However, in Equation 8, 0.220 <x <0.350
(Equation 9)
y = 737462.022 × x ⁶ −1267177.816 × x ⁵ + 904622.642 × x ⁴ −343495.090 × x ³ +73 187.274 × x ² −8299.969 × x + 392.073
However, in Equation 9, 0.210 <x <0.350

  Among the above combinations, the first green pigment is a kind selected from green pigments for color filters capable of displaying the region B, and the second green pigment is a green pigment for color filters capable of displaying the region C. Is particularly preferable from the viewpoints of approaching the color of each standard green pixel with a relatively small amount of pigment used, increasing the luminance, reducing the film thickness, and widening the color reproduction range.

  In addition, when displaying a green pixel having a strong bluish color and a wide color gamut such as NTSC and EBU standards, it is preferable that the amount of the first green pigment is larger than the amount of the second green pigment. When displaying a green pixel with strong yellowness and high brightness as in the sRGB standard, the amount of the second green pigment is preferably larger than the amount of the first green pigment.

  As the green pigment in the coloring component of the present invention, the above-described sufficient effect can be obtained even if it is composed of only the first and second green pigments. A fourth pigment such as a fourth green pigment may further contain a plurality of pigments. Even in such a case, the third or more green pigment is separated from the first green pigment or the second green pigment in the xy chromaticity coordinate region because the effect of expanding the color reproduction range is increased. Specifically, when each pigment is fixed at y = 0.50 on the xy chromaticity coordinates, each x is 0.02 or more, preferably 0.03 to 0.05 apart. Preferably it is. The third or more green pigment may be selected from the above regions A and C, or may be selected from another region.

  The total blending amount of the green pigment for the color filter that can display the region A and the region C including the first and second green pigments, and optionally including the third or more green pigments, is a wide color reproduction range and high brightness color. From the point of forming a green pixel of the filter, it is more than 30% by mass based on the total amount of coloring components in the photosensitive coloring composition according to the present invention, and more than 39% by mass, depending on the target color coordinates, more than 50% by mass. It is preferable that many are included.

  In addition, the total amount of the green pigment for color filter that can display the region A and the region C including the first and second green pigments, and optionally including the third or more green pigments, has a wide color reproduction range and high brightness. From the point of forming the green pixel of the color filter, it is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more based on the total amount of the green pigment in the coloring component in the photosensitive coloring composition. Further, depending on the target color coordinates, there may be a case where the amount of the green pigment not belonging to the region A and the region C is extremely small or not sufficient, and the first and second green pigments are included. The total blending amount of the green pigment for a color filter capable of displaying the above-mentioned green pigment-containing region A and region C is 80% by mass or more based on the total amount of the green pigment, and even if it is 100% by mass, the target color coordinates It is possible to adjust to.

  Further, by combining at least one yellow pigment together with a green pigment in the coloring component, it is possible to reduce the transmittance of the spectral transmittance spectrum at a wavelength of 380 to 470 nm. Examples of yellow pigments include C.I. I. Pigment Yellow (PY) 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, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 85, 187, 199, etc. are mentioned, but PY83, 138, 139, 150, 185 are preferred from the viewpoint of high luminance or a small amount of pigment and suitable for thinning, and particularly PY138, 150, 185 is preferred. preferable. These can be used alone or in combination of two or more.

  Both the first and second green pigments used in the present invention have a low spectral transmittance spectrum at a wavelength of 380 to 470 nm as compared with the conventional green pigment, and the first green pigment is sufficiently green. In the photosensitive coloring composition for a color filter according to the present invention, the amount of yellow pigment used is reduced because the second green pigment has a strong yellowish color while being relatively colored. Less. When a photosensitive coloring composition is prepared by mixing a yellow pigment, the mixing ratio of the yellow pigment to the total amount of the green pigment including the first and second green pigments is expressed by a mass ratio (yellow pigment / green pigment). Even when it is preferably 1.6 or less, more preferably 0.8 or less, the transmittance of the spectral transmittance spectrum at a wavelength of 380 to 470 nm can be sufficiently reduced. Furthermore, since both of the first and second green pigments have a low spectral transmittance spectrum at a wavelength of 380 to 470 nm, the transmittance can be sufficiently reduced even when a highly transparent yellow pigment is combined. it can. In this case, the luminance of the pixel after toning can be increased.

  Both the first and second green pigments have excellent coloring power and high transmittance, and the second green pigment has a strong yellowish tint. Sufficient color development can be obtained. When toning the first and second green pigments as the center of the coloring component, the amount of yellow pigment used in combination as described above can be reduced, the amount of the entire pigment used is reduced, and the transparency is high. The photosensitive coloring composition which can form the green pixel excellent in color purity is obtained. In addition, since many yellow pigments are inferior in heat resistance and light resistance, the amount of the yellow pigment used is reduced, so that the resistance of the obtained green pixel is improved.

  In order to obtain an image display device having a large color gamut, particularly when a high density type (high color density type) color filter is required, a photosensitive coloring composition having a very high pigment ratio (high density type photosensitive coloring) Composition) is often used. However, since the high-concentration photosensitive coloring composition has a large pigment content, the influence on the optical performance such as transparency, fine pattern formation ability, and film physical properties other than color density is particularly serious when pixels are formed. It becomes. On the other hand, the photosensitive coloring composition of the present invention can provide a color that can sufficiently correspond to the high concentration type even with a very small amount of pigment as the high concentration type photosensitive coloring composition. For example, even when the pigment (P) / vehicle (V) ratio (mass ratio) is in the range of 0.25 to 1.0, preferably in the range of 0.25 to 0.8, a green pixel having high density and high transparency is formed. it can. In the present invention, the P / V ratio pigment (P) is the total amount of the coloring component, that is, the pigment contained in the photosensitive coloring composition according to the present invention, and the first and second green colors. Other pigments such as a yellow pigment mixed with the pigment are included, and the vehicle means a non-volatile component excluding the pigment in the photosensitive coloring composition, and a liquid monomer component is also included in the vehicle.

  Further, as the amount of pigment used decreases, the amount of pigment used can be reduced when a dispersant for dispersing the pigment is used. Therefore, a photosensitivity composed of components that do not participate in the curing reaction (non-reactive components) such as pigments and dispersants and components (reactive components) that participate in the curing reaction such as photocurable resins, initiators, and thermosetting resins. When a pixel is formed using a reactive coloring composition, the blending ratio of non-reactive components decreases and the blending ratio of reactive components increases. Specifically, in the photosensitive coloring composition according to the present invention, the mass ratio (b / a) of the non-reactive component (b) other than the coloring component to the reactive component (a) is 0.45 or less. And sufficient reactivity can be obtained. Here, the non-reactive component other than the coloring component is mainly composed of a dispersant. Therefore, if sufficient pigment dispersibility can be obtained, the smaller the mass ratio (b / a), the smaller the amount of dispersant used, and the higher the proportion of reactive components in the photosensitive coloring composition. As a result, the photocurability is improved, and a green pixel excellent in various physical properties such as hardness, elasticity, film thickness uniformity, suppression of chipping, residue reduction, developability improvement, crosslinking density improvement, thinning, and the like is obtained.

  When preparing the photosensitive coloring composition according to the present invention, the pigment may be prepared in advance in a pigment dispersion, and the resulting pigment dispersion and the reactive component may be mixed. In this case, a photosensitive coloring composition having good pigment dispersibility can be obtained.

  As the dispersant for preparing the pigment dispersion, the following polymer dispersants, that is, (meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (Kyoeisha Oils and Fats) Chemical industry), Megafuck F171, F172, F173 (Dainippon Ink and Chemicals), Florard Fc430, Fc431 (Sumitomo 3M), Solsperse 13240, 20000, 24000, 26000, 28000, etc. ), Dispersic 111, 161, 162, 163, 164, 182, 2000, 2001, etc. Dispersic dispersants (by Big Chemie), Ajisper PB711, PB411, PB111, PB821, PB822 Techno) or the like can be used.

  Surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine can also be used as the dispersant. Among surfactants, polymer surfactants as exemplified below, that is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl Polyoxyethylene alkyl phenyl ethers such as phenyl ether and polyoxyethylene nonyl phenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid-modified polyesters; Tertiary amine-modified polyurethane High molecular surfactants such as those are preferably used.

  The blending ratio of the dispersant is usually 100 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the coloring component (the total of the green pigment and other pigments).

  As a solvent (dispersion solvent) for preparing the pigment dispersion, various organic solvents used as a dilution solvent for preparing a photosensitive coloring composition described later can be used. The dispersion solvent is usually used in a proportion of 100 to 1000 parts by mass, preferably 200 to 900 parts by mass with respect to 100 parts by mass of the coloring component (the total of the green pigment and other pigments).

  In the pigment dispersion, a green pigment, other pigments, a dispersant, and other components as necessary are mixed in a solvent in any order, and a jet mill, a kneader, a roll mill, an attritor, a super mill, a dissolver, a homogen, It can prepare by disperse | distributing using well-known dispersers, such as a mixer and a sand mill. The pigment may be prepared as a dispersion separately for each pigment, or may be prepared as a dispersion by mixing.

  The photosensitive coloring composition according to the present invention is a component involved in photocuring, such as a photopolymerizable compound and a photopolymerization initiator, together with the first and second green pigments and, if necessary, other pigments and a dispersant. That is, it is prepared by blending a reactive component and appropriately diluting with a solvent as necessary.

  A photopolymerizable compound is a compound that cures itself by a direct polymerization reaction upon irradiation with light, or a polymerization reaction that occurs under the action of an initiator activated by irradiation with light. The reaction form of the photopolymerizable compound may be any of radical polymerization, anionic polymerization, cationic polymerization, etc., but the photopolymerizable compound is usually a radical polymerizable monomer, oligomer or polymer having an ethylenically unsaturated bond. Is used.

  As the monomer or oligomer having an ethylenically unsaturated bond, a polyfunctional acrylate monomer or oligomer is preferably used. For example, ethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri ( (Meth) acrylate, glycerin tetra (meth) acrylate, tetratrimethylolpropane tri (meth) acrylate, 1,4-butanedioldia Relate, pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol (meth) acrylate, and the like can be exemplified dipentaerythritol hexa (meth) acrylate. These components may be used in combination of two or more.

  At least a part of the monomer or oligomer preferably has two or more radically polymerizable groups and particularly preferably three or more in order to obtain a sufficient crosslinking density.

  Examples of the polymer having an ethylenically unsaturated bond include a polymer molecule obtained by polymerizing a polymer of the above polyvalent acrylate monomer, or a monomer having another functional group such as a hydroxyl group or a carboxyl group together with the ethylenically unsaturated bond. A polymer in which an ethylenically unsaturated bond is introduced using another functional group such as a hydroxyl group or a carboxyl group present as a scaffold can be used.

  In order to obtain sufficient film-forming properties, it is desirable to use a polymerizable polymer, and in order to obtain a sufficient crosslinking density, it is desirable to use a polymerizable monomer or oligomer. Is preferred.

  The binder resin comprising these polymerizable or non-polymerizable polymer and / or polymerizable monomer and / or oligomer is usually 5 to 15% by mass, preferably 7 as a solid content ratio in the photosensitive coloring composition. Contained in an amount of 10 to 10% by mass.

  As the photopolymerization initiator, a compound that generates an active species that initiates a polymerization reaction such as radical polymerization, anion polymerization, or cationic polymerization by light irradiation can be used, and an appropriate compound is used depending on the reaction mode of the photopolymerizable compound. Choose one that generates active species. As the photoradical initiator, ultraviolet rays, ionizing radiation, visible light, or other compounds that generate free radicals at various wavelengths, particularly energy rays of 365 nm or less, are used. For example, benzophenone derivatives such as benzoin and benzophenone or the like Derivatives such as esters; xanthone and thioxanthone derivatives; halogen-containing compounds such as chlorosulfonyl, chloromethyl polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethyl benzophenones; triazines; fluorenones; haloalkanes; Redox couples of dye and reducing agent; organic sulfur compounds; peroxides. Preferably, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 907 (all manufactured by Ciba Specialty Chemicals), Darocur (Merck), Adeka 1717 (Asahi Denka Kogyo Co., Ltd.), 2, Examples include ketone-based and biimidazole-based compounds such as 2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (manufactured by Kurokin Kasei Co., Ltd.). be able to. These initiators can be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable not to inhibit the absorption spectral characteristics.

  The photo radical initiator is usually contained in the photosensitive coloring composition in a solid content ratio of 0.05 to 18% by mass, preferably 0.1 to 13% by mass. When the addition amount of the photo radical initiator is less than 0.05% by mass, the photocuring reaction does not proceed, and the remaining film ratio, heat resistance, chemical resistance, and the like tend to decrease. Further, when this added amount exceeds 18% by mass, the solubility in the base resin reaches saturation, and crystals of the initiator are precipitated during spin coating or coating leveling, and the uniformity of the film surface cannot be maintained. There arises a problem of film roughness.

  In preparing the photosensitive coloring composition, the photopolymerization initiator may be added to the photosensitive coloring composition according to the present invention from the beginning. It is preferable to disperse or dissolve in the photosensitive resin composition immediately before.

  Furthermore, in the photosensitive coloring composition of the present invention, a compound having two or more epoxy groups in the molecule (if necessary) for the purpose of improving heat resistance, adhesion, and chemical resistance (particularly alkali resistance) ( Epoxy resin) can be blended. Examples of compounds having two or more epoxy groups in the molecule include bisphenol F type epoxy resins such as Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 (made by Yuka Shell) as bisphenol A type epoxy resins. Epicote 807 (manufactured by Yuka Shell), such as EPPN201, 202 (manufactured by Nippon Kayaku), phenol novolac-type epoxy resin, EOCN102, 103S, 104S, 1020 as cresol novolak-type epoxy resin, such as Epikote 154 (manufactured by Yuka Shell) Examples thereof include 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.) and Epicoat 180S (manufactured by Yuka Shell). Furthermore, cycloaliphatic epoxy resin and aliphatic polyglycidyl ether can also be illustrated.

  Such an epoxy resin is usually contained in the photosensitive coloring composition in a solid content ratio of 0 to 60% by mass, preferably 5 to 40% by mass.

  In addition to the above-described components, various additives such as a silane coupling agent can be blended with the photosensitive coloring composition as necessary.

The photosensitive coloring composition usually has good solubility in compounding components such as a photopolymerizable compound, a polyvalent radical polymerizable compound, and a photopolymerization initiator in consideration of coating and applicability, and spin. A solvent having a relatively high boiling point is contained so that the coating property is good. Examples of usable solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; carbs such as methoxyethoxyethanol and ethoxyethoxyethanol. Toll solvents; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone, cyclohexanone; methoxyethyl acetate, ethoxyethyl acetate, ethyl Cellosolve acetate solvents such as cellosolve acetate; Carbitol acetates such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate Solvents; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; and γ-butyrolactone Examples include lactone solvents; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; and organic solvents such as saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Ether solvents such as glycol diethyl ether; aprotic amide solvents such as N, N-dimethylacetamide; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are particularly preferably used. Particularly preferably, N, N-dimethylacetamide, MBA (3-methoxybutyl acetate, CH ₃ CH (OCH ₃ ) CH ₂ CH ₂ OCOCH ₃ ), PGMEA (propylene glycol monomethyl ether acetate, CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), DMDG (diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ) or a mixture thereof can be used, and the solid content concentration is adjusted to 10 to 70% by mass using these.

  In order to produce the photosensitive coloring composition, the first and second green pigments, other pigments and dispersants, photopolymerizable compounds, photopolymerization initiators, and other components as appropriate are appropriately used. A pigment dispersion composed of the first and second green pigments, other pigments, a dispersing agent, and the like, a photosensitive component such as a photopolymerizable compound and a photopolymerization initiator, and other components are added to the solvent. It may be put in and dissolved and dispersed by a general method such as paint shaker, bead mill, sand grind mill, attritor mill, 2-roll mill, 3-roll mill, kneader.

  A green pixel of a color filter can be formed using the photosensitive coloring composition thus obtained. The color filter includes a black matrix formed in a predetermined pattern on a transparent substrate and a pixel portion formed in a predetermined pattern on the black matrix, and is formed to cover the pixel portion as necessary. A protective film is provided. A transparent electrode for driving liquid crystal may be formed on the protective film as necessary. In addition, a spacer may be formed on the transparent electrode plate, the pixel portion, or the protective film in accordance with the region where the black matrix layer is formed.

  The pixel portion includes red pixels, green pixels, and blue pixels arranged in a desired pattern such as a mosaic type, a stripe type, a triangle type, or a four-pixel arrangement type. Is provided in a predetermined area outside the.

  The green pixel can be formed by applying the photosensitive coloring composition of the present invention to one side of a transparent substrate, exposing it by irradiating with light through a photomask, heat-curing in a clean oven or the like after alkali development. . The colored layers such as other color pixels and the black matrix layer are preferably formed by the pigment dispersion method as in the case of the green pixels, but may be formed by other methods such as a dyeing method, a printing method, and an electrodeposition method. it can. The black matrix layer may be formed by chromium vapor deposition or the like. The pixel portion is usually formed to a thickness of about 2.0 μm.

  The protective film can be formed by applying a coating liquid of a transparent photosensitive resin composition by a method such as a spin coater, a roll coater, spraying or printing. The protective film is formed to a thickness of about 2 μm, for example. When using a spin coater, the number of revolutions is set within a range of 500 to 1500 revolutions / minute. The coating film of the photosensitive resin composition is exposed by irradiating activation energy rays through a photomask, and after alkali development, it is heated and cured in a clean oven or the like to form a protective film.

  The transparent electrode on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and their alloys, etc., such as sputtering, vacuum deposition, CVD, etc. This is formed by a simple method, and is formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.

  The spacer on the transparent electrode is also coated with a coating solution of the photosensitive resin composition by a method such as spin coater, roll coater, spray, printing, etc., exposed by activation energy ray irradiation through a photomask, and after alkali development It can be formed by heat curing in a clean oven or the like. The spacer is preferably a columnar spacer having a height corresponding to the cell gap. The columnar spacer is formed with a height of about 5 μm, for example. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film.

  For the alignment film, a coating liquid containing a resin such as polyimide resin is applied to the inner surface of the color filter by a known method such as spin coating, dried, and cured by heat or light as necessary, and then rubbed. Can be formed.

  The color filter thus obtained includes a transparent substrate and a pixel portion formed on the transparent substrate, and should further face a black matrix layer, a protective film covering the colored layer and / or face as necessary. In order to maintain the distance from the electrode substrate, a spacer or the like provided at a position overlapping with the non-display portion may be provided, and the green pixel in the pixel portion is formed using the photosensitive coloring composition of the present invention. Is.

  This green pixel has a film thickness of 2.5 μm or less, and when the color is measured with a single pixel, the x coordinate is 0.25 ≦ x ≦ 0.32 and the y coordinate is 0.55 ≦ when the CIE XYZ color system is used. A color space in the range of y ≦ 0.75 and stimulation value Y of 30 ≦ Y, more preferably 40 ≦ Y, and even more preferably 50 ≦ Y can be displayed, and a wide color reproduction region can be obtained by combining with other color pixels. It can be secured, and the film thickness is thin and the brightness is very high.

  In addition, the green pixel can be strengthened in yellow by simply mixing a small amount of yellow pigment, and the mass ratio of the yellow pigment to the total amount of the green pigment in the pixel (yellow pigment / green pigment) is 1. Even in the case of .6 or less, when the color is measured with a single pixel, the x coordinate is in the range of 0.25 ≦ x ≦ 0.32 and the y coordinate is in the range of 0.55 ≦ y ≦ 0.75 in the CIE XYZ color system. The xy chromaticity coordinate area can be displayed.

  In addition, the green pixel has less non-reactive components such as pigments and dispersants, photosensitive components such as photopolymerizable compounds and photopolymerization initiators, and curable components other than photosensitive components such as thermosetting resins. , Because it is possible to increase the proportion of reactive components including developable components such as alkali-soluble binder, photocurability, fine pattern forming ability, physical properties after pixel formation, specifically, Irradiation sensitivity is good, residue is hardly generated, foreign matter is not left, the degree of development is high, the shape after development is accurate, the cross section of the pixel is trapezoidal, and the film thickness is uniform. In addition, the resulting pixels have high crosslink density, so they are excellent in hardness and elasticity and have little impurity elution.

  According to the present invention, when the coating film of the photosensitive coloring composition is exposed from the upper surface, it is sufficiently cured to the lower side of the coating film. The ratio of the length of the upper base to the height (upper base / lower base) is formed in a tapered shape with a value of less than 1, and the pattern shape is good.

Further, the obtained pixel has a hardness of 500 N / mm ² or more or an elastic deformation rate of 20% or more, and a green pixel that is difficult to deform is obtained.

The hardness of the pixel was measured using an ultra-micro hardness meter (WIN-HCU manufactured by Fisher Instruments Co., Ltd.). ) As the universal hardness (test load / surface area of the Vickers indenter under the test load: N / mm ² ) when the surface hardness is measured.

  Also, the elastic deformation rate is specified as a ratio of the elastic deformation amount to the total deformation amount, which is the sum of the elastic deformation amount and the plastic deformation amount, by measuring the elastic deformation amount and the plastic deformation amount in the above test.

  In addition, liquid crystal color televisions require high-speed response in order to support moving images. In response to such a requirement, a sufficient amount of the curing component can be used by using the photosensitive coloring composition of the present invention, so that the elution of impurities is reduced, and a color filter excellent in voltage holding ratio is produced. Applicable to LCD color TV.

  A liquid crystal panel is obtained by making the color filter manufactured in this way face the liquid crystal driving side substrate which is a counterpart member and filling the gap with liquid crystal and sealing. Such a liquid crystal panel can be suitably applied as a display device such as a flat display such as a personal computer.

  Although the color filter for the liquid crystal display device has been described as a representative example of the color filter according to the present invention, the present invention can be applied to an active color filter regardless of the drive mode such as TN, IPS, and VA. In addition, the present invention is not limited to the active method, and can be applied to various color filters for driving methods such as a simple matrix method. ) Applicable to device color filters.

  The EL device can arrange full color display by arranging the EL elements of RGB colors in a matrix and control the light emission of each color, but by arranging a color filter on the light extraction side (viewer side) of the EL elements, The display performance can be improved by modulating the colored light, and the color filter protects the EL element from the external light and contributes to a longer life.

A. Synthesis of Green Pigment (Synthesis Example 1): First Green Pigment Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 600-700 nm. For halogenation, 3.1 parts by mass of sulfuryl chloride, 3.7 parts by mass of anhydrous aluminum chloride, 0.46 parts by mass of sodium chloride, and 1 part by mass of zinc phthalocyanine were mixed at 40 ° C., and 2.2 parts by mass of bromine was added dropwise. I went. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 2.6 parts by mass of a purified brominated zinc phthalocyanine crude pigment.

  1 part by weight of this brominated zinc phthalocyanine crude pigment, 7 parts by weight of crushed sodium chloride, 1.6 parts by weight of diethylene glycol and 0.09 parts by weight of xylene were charged into a double arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts by mass of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and ground to obtain a brominated zinc phthalocyanine pigment (hereinafter referred to as pigment composition (1)).

The obtained brominated zinc phthalocyanine pigment was (Pc: phthalocyanine) with an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ from the halogen content analysis by mass spectrometry. The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

(Synthesis Example 2): Second green pigment Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. This 1-chloronaphthalene solution had light absorption at 600 to 700 nm. For halogenation, 3.1 parts by mass of sulfuryl chloride, 3.7 parts by mass of anhydrous aluminum chloride, 0.46 parts by mass of sodium chloride, and 1 part by mass of zinc phthalocyanine were mixed at 40 ° C., and 4.4 parts by mass of bromine was added dropwise. I went. The mixture was reacted at 80 ° C. for 15 hours, and then the reaction mixture was poured into water to precipitate a brominated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 80 ° C., and dried at 90 ° C. to obtain 3.0 parts by mass of a purified brominated zinc phthalocyanine crude pigment.

  1 part by weight of this brominated zinc phthalocyanine crude pigment, 7 parts by weight of crushed sodium chloride, 1.6 parts by weight of diethylene glycol and 0.09 parts by weight of xylene were charged into a double arm kneader and kneaded at 100 ° C. for 6 hours. After kneading, it was taken out into 100 parts by mass of water at 80 ° C., stirred for 1 hour, and then filtered, washed with hot water, dried and pulverized to obtain a brominated zinc phthalocyanine pigment (hereinafter referred to as pigment composition (2)).

The obtained brominated zinc phthalocyanine pigment was found to have an average composition of ZnPcBr ₁₄ Cl ₂ (Pc; phthalocyanine) and an average of 14 bromine atoms in one molecule based on halogen content analysis by mass spectrometry. The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

B. Preparation of green pigment dispersion (dispersion 1)
15 parts by mass of the pigment composition (1) synthesized in Synthesis Example 1 and an acrylic dispersant manufactured by Big Chemie Co., Ltd. in a high-speed disperser “TSC-6H” manufactured by Igarashi Machinery Co., Ltd. charged with zirconia beads having a diameter of 0.5 mm. 7 parts by mass of “BYK-2001” and 78 parts by mass of propylene glycol monomethyl acetate (hereinafter referred to as PGMEA) were charged and stirred at 2000 rpm for 8 hours to prepare a brominated zinc phthalocyanine pigment dispersion (1). . After the preparation, spectral transmittance spectrum measurement, particle size distribution measurement, and viscosity measurement were performed. Each evaluation result is shown in Table 1. Further, FIG. 5 shows a monochromatic spectral transmittance spectrum in which the wavelength (Tmin) at which the transmittance is minimized is 5%, together with the monochromatic spectral transmittance spectra of PG7 and PG36, which are conventional green pigments.

a) Spectral Transmittance Spectrum Measurement The monochromatic spectral transmittance spectrum was measured using an OSP-SP200 microspectrophotometric device manufactured by Olympus Corporation. The measurement conditions were as follows: the light source was F10 light source, the illumination magnification was 20 times, and the pinhole No. 7 (50 μm).

b) Viscosity measurement The viscosity at 23.5 ° C. was measured using a rotational vibration viscometer (Viscomate VM-1G, manufactured by Yamaichi Electronics Co., Ltd.).

c) Particle size distribution measurement 0.1 parts by mass of the pigment dispersion was diluted with 9.9 parts by mass of the PGMEA solvent, and the particle size distribution was measured using a Microtrac UPA particle size distribution meter (manufactured by Nikkiso Co., Ltd.).

(Dispersion 2)
A brominated zinc phthalocyanine pigment dispersion (2) was prepared and evaluated in the same manner as dispersion 1, except that pigment composition (2) was used instead of pigment composition (1). . Each evaluation result is shown in Table 1.

(Dispersion comparison 1)
A chlorinated copper phthalocyanine pigment dispersion was prepared in the same manner as Dispersion 1 except that Pigment Green 7 (chlorinated copper phthalocyanine pigment) was used instead of Pigment Composition (1), and evaluated in the same manner as Dispersion 1. did. Each evaluation result is shown in Table 1.

(Dispersion comparison 2)
A brominated copper phthalocyanine pigment dispersion was prepared in the same manner as Dispersion 1 except that Pigment Green 36 (brominated copper phthalocyanine pigment) was used instead of Pigment Composition (1), and evaluated in the same manner as Dispersion 1. did. Each evaluation result is shown in Table 1.

  In the dispersions 1 and 2 used in the coloring composition of the present invention, the transmittance of the spectral transmittance spectrum at 435 nm, which is the wavelength of the blue light source of the F10 light source, is lower than that of PG7, and the blue component to be erased by toning It became clear that it was decreasing. Furthermore, the transmittance at 490 nm, which is the sub-wavelength of the three-wave tube of the F10 light source, is lower than that of PG7 and PG36 and does not pass through the sub-wavelength light source of the F10 light source. Moreover, it became clear that the transmittance | permeability in 545 nm is high compared with PG7, and has the high transmittance | permeability in 545 nm vicinity which is a green wavelength. Moreover, the transmittance | permeability in 610 nm was low compared with PG36, and it became clear that the reddish component has decreased. In addition, it has been clarified that in dispersions 1 and 2, chromaticity coordinate regions that cannot be displayed by PG7 and PG36 can be displayed, and the Y value is relatively high, that is, the brightness is high.

  Dispersions 1 and 2 had lower viscosity and better dispersibility than PG7 and PG36. Further, in the dispersions 1 and 2, since the average particle size (50% particle size) was smaller than that of PG7 and PG36, it was found that the dispersions 1 and 2 were finer and the dispersibility was good.

C. Preparation of photosensitive green composition (photosensitive green composition example 1)
(1) Preparation of yellow pigment dispersion A PY150 pigment dispersion was prepared in the same manner as dispersion 1, except that PY150 was used instead of pigment composition (1).

(2) Preparation of photosensitive green composition A To prepare an alkali-soluble reactive polymer, 70 parts by mass of MMA, 15 parts by mass of BzMA, 15 parts by mass of MAA, and 100 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) PGMEA were added to the flask. The polymerization was carried out for 7 hours at 93 ° C. in a nitrogen atmosphere. The solid content concentration of the reaction solution was adjusted to 40.2% with PGMEA. The acid value of the obtained polymer was 104 mg / KOH, and the weight average molecular weight Mw in terms of polystyrene was 24,700.

  Next, brominated zinc phthalocyanine dispersions (1) and (2), PY150 pigment dispersion, alkali-soluble photoreactive polymer, dipentaerythritol pentaacrylate (hereinafter referred to as DPPA), Irgacure 369 (trade name) and PGMEA The photosensitive green composition A was prepared by stirring at room temperature and filtering at the following blending ratio.

<Composition of photosensitive green composition A>
Brominated zinc phthalocyanine pigment dispersion (1): 11.20 parts Brominated zinc phthalocyanine pigment dispersion (2): 7.47 parts PY150 pigment dispersion: 28.00 parts Alkali-soluble photoreactivity Polymer: 8.16 parts, DPPA (Sartomer SR399E manufactured by Nippon Kayaku Co., Ltd.): 4.22 parts, Irgacure 369 (trade name: manufactured by Ciba Specialty Chemicals)
: 3.21 parts · PGMEA: 37.75 parts

(Photosensitive green composition example 2 and photosensitive green composition comparative examples 1-4)
Photosensitive green compositions B to F were prepared in the same procedure as in photosensitive green composition example 1 except that the blending components were changed as shown in Table 2.

(Photosensitive Green Composition Example 3)
(1) Preparation of Yellow Pigment Dispersion A PY83 pigment dispersion was prepared in the same manner as Dispersion 1, except that PY83 was used instead of the pigment composition (1).

(2) Preparation of photosensitive green composition G Brominated zinc phthalocyanine pigment dispersions (1) and (2), PY83 pigment dispersion, the same alkali-soluble photoreactive polymer as in Example 1, dipentaerythritol pentaacrylate (Hereinafter, DPPA), Irgacure 369 (trade name) and PGMEA were mixed, stirred and filtered at the following ratios at room temperature to prepare photosensitive green composition G.

<Composition of photosensitive green composition G>
Brominated zinc phthalocyanine pigment dispersion (1): 31.71 parts Brominated zinc phthalocyanine pigment dispersion (2): 20.18 parts PY83 pigment dispersion: 5.76 parts Alkali-soluble photoreactivity Polymer: 6.31 parts / DPPA (Nippon Kayaku Co., Ltd. Sartomer SR399E): 3.26 parts / Irgacure 369 (trade name: Ciba Specialty Chemicals)
: 2.49 parts · PGMEA: 30.29 parts

(Photosensitive green composition comparative examples 5-8)
Photosensitive green compositions H to K were prepared in the same procedure as in photosensitive green composition example 1 except that the blending components were changed as shown in Table 3.

D. Formation of Green Pixel (Green Pixel Examples 1-2, Green Pixel Comparative Examples 1-4)
Green pixels were prepared using the photosensitive green composition A of Examples and the photosensitive green compositions B to F of Comparative Examples, and the following items were evaluated. The evaluation results are shown in Table 4.

(1) Formation of Green Pixel A photosensitive green composition was applied and dried on a 10-cm glass substrate with a spin coater (manufactured by MIKASA, model 1H-DX2) to form a coating film. This coating film was heated on a hot plate at 90 ° C. for 3 minutes. After the heating, ultraviolet rays were irradiated through a photomask at an intensity of 100 mJ / cm ² (converted to 405 nm illuminance) by a UV aligner (Dainippon Screen, model MA 1200) equipped with a 2.0 kW ultrahigh pressure mercury lamp. After irradiating with ultraviolet light, developed with a 0.5 mass% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed with a spin developer, washed with pure water for 1 minute and dried, and the coating film was cleaned in a clean oven. The cured film was obtained by drying at 230 ° C. for 30 minutes using a SCOV-250 Hy-So).

(2) Color evaluation The color filter pixel thus formed was measured with an OSP-SP200 microspectrophotometer by Olympus Corporation. The measurement conditions were as follows: the light source was F10 light source, the illumination magnification was 20 times, and the pinhole No. 7 (50 μm).
Table 4 shows the thickness of each cured film with color evaluation of x = 0.310 and y = 0.630. Each of the items was evaluated thereafter using a coating film and a cured film where x = 0.310 and y = 0.630 in the color evaluation.

(3) Hardness / Elastic Deformation Rate Evaluation The hardness of the obtained cured film was measured under the condition that the maximum load of the Vickers indenter was 20 mN using an ultra-micro hardness meter (WIN-HCU manufactured by Fisher Instruments Co., Ltd.). Was evaluated by universal hardness (test load / surface area of Vickers indenter under test load: N / mm ² ).
Moreover, from the deformation amount at the maximum load and the deformation amount after releasing the load simultaneously measured, the following formula:
Elastic deformation rate = 100− (deformation amount after releasing load / deformation amount at maximum load) × 100
According to this, the elastic deformation rate was calculated.

(4) Evaluation of residue, sensitivity, adhesion, developability and cross-sectional shape An ultrahigh pressure mercury lamp is applied to each coating film in which the cured film has x = 0.310 and y = 0.630 in the color evaluation of (2). Ultraviolet rays including wavelengths of 365 nm, 405 nm, and 436 nm were irradiated through the photomask used at an exposure amount of 300 mJ / cm ² . However, when performing the sensitivity evaluation, the exposure amount was varied in the range of 50 to 300 mJ / cm ² . Thereafter, each substrate was developed with a spin developing machine for 1 minute using a 0.5 wt% potassium hydroxide aqueous solution at 23 ° C., washed with pure water for 1 minute, and dried. Thereafter, the substrate was post-baked in a 230 ° C. clean oven for 30 minutes to produce a pixel array in which pixel patterns were arranged on the substrate. Moreover, the following evaluation was performed about the obtained green pixel. The results are shown in Table 4.

<Residue>
The substrate surface of the unexposed part was wiped 10 times with a lens cleaner containing ethanol (trade name Toraysee, manufactured by Toray Industries, Inc.), the lens cleaner was examined for coloring, and evaluated according to the following criteria.
○: The lens cleaner is not colored at all.
*: The lens cleaner is colored.

<Sensitivity>
The minimum exposure amount at which a 20 μm line & space was in close contact was measured and evaluated according to the following criteria.
○: A 20 μm line adheres at 100 mJ / cm ² or less.
-X: 100 mJ / cm ² or less and 20 μm line does not adhere.

<Adhesion>
The minimum line width that was in close contact with the line and space of 1 μm to 50 μm without being flowed after the development process was measured and evaluated according to the following criteria.
○: A line of 10 μm or less adheres.
X: Lines of 10 μm or less do not adhere.

<Developability>
The time when the unexposed part was completely dissolved was measured and evaluated according to the following criteria.
-: It completely dissolves in 20 to 40 seconds.
○: Completely dissolved within 60 seconds.
X: Not completely dissolved within 60 seconds.

<Cross sectional shape>
The pixels produced on the substrates in Examples 1 and 2 and Comparative Examples 1 to 4 were cut along with the glass substrate perpendicular to the lines and spaces, and a cross-sectional photograph from the side was taken with a scanning electron microscope. The magnification was 10,000 times. On the photograph taken, the length of the upper base and the lower base of the pixel cross section was measured, and the ratio of the length of the upper base to the length of the lower base (upper base / lower base) was obtained. The obtained ratio was evaluated according to the following criteria.
○: The ratio is less than 1.
*: Ratio is 1 or more.

  Examples 1 and 2 which are photosensitive coloring compositions according to the present invention have thin film thicknesses of 1.85 μm and 2.15 μm, and x in the XYZ color system of CIE when colorimetry is performed with a single pixel. The coordinates were 0.310, the y coordinate was 0.630, and the stimulus values Y were 55.7 and 56.2, which were high in luminance. Even when the mass ratio of the yellow pigment to the green pigment (yellow pigment / green pigment) is 1.6 or less, the x coordinate is 0.310 in the CIE XYZ color system when the color is measured with a single pixel, and the y coordinate is An xy chromaticity coordinate area in the range of 0.630 could be displayed. Examples 1 and 2, which are photosensitive coloring compositions according to the present invention, have thin film thicknesses of 1.85 μm and 2.15 μm, and hardness, elastic deformation rate, residue, sensitivity, adhesion, developability, and shape. Excellent pixels were also obtained at.

  On the other hand, Comparative Example 1 using PG7 as the green pigment needs to contain a lot of yellow pigment / green pigment = 3.5 and yellow pigment in order to realize the same chromaticity (x, y) as Example 1. The film thickness was 2.55 μm, and the obtained stimulation value Y was 51.0, which was a relatively dark pixel. Moreover, since the film thickness was thick, it was inferior to a residue, adhesiveness, and developability.

  Further, in Comparative Example 2 using PG36 as a green pigment, in order to realize the same chromaticity (x, y) as in Example 1, it is necessary to increase the film thickness to 2.83 μm, and the luminance is also implemented. It was inferior to Examples 1 and 2. Further, since the film thickness is thick, the hardness, elastic deformation rate, residue, sensitivity, adhesion, developability, and shape are all inferior.

  In Comparative Examples 3 and 4 using PG7 and PG36 in combination as green pigments, the film thickness is improved over PG36 in order to achieve the same chromaticity (x, y) as in Example 1. Although it was necessary to increase the thickness, the luminance was improved as compared with PG7, but it was inferior to the example. Moreover, since the film thickness was thick, it was inferior to a residue, adhesiveness, and developability.

(Green Pixel Example 3, Green Pixel Comparative Examples 5 to 8)
Green pixels were prepared using the photosensitive green composition G of the example and the photosensitive green compositions H to K of the comparative examples, and the same items as in Example 1 were evaluated in the same manner. Table 5 shows the thickness of each cured film with color evaluation of x = 0.257 and y = 0.963. Each item was evaluated using a coating film and a cured film in which x = 0.257 and y = 0.963 in color evaluation. The evaluation results are shown in Table 5.

  In Example 3 which is a photosensitive coloring composition according to the present invention, the film thickness is as thin as 2.45 μm, and the x coordinate in the XYZ color system of CIE when colorimetry is performed with a single pixel is 0.257, The y coordinate was 0.693, and the stimulus value Y was 31.9, which was high in luminance. Example 3 which is a photosensitive coloring composition according to the present invention has a thin film thickness, and an excellent pixel is obtained in terms of hardness, elastic deformation rate, residue, sensitivity, adhesion, developability, and shape.

  On the other hand, Comparative Example 5 using PG7 as a green pigment needs to contain many yellow pigments / yellow pigment / green pigment = 0.9 in order to achieve the same chromaticity (x, y) as Example 3. The film thickness was 2.93 μm, and the obtained stimulation value Y was 24.6, which was a relatively dark pixel. Moreover, since the film thickness was thick, the residue and developability were poor.

  Further, in Comparative Example 6 using PG36 as the green pigment, in order to realize the same chromaticity (x, y) as in Example 3, the film thickness needs to be increased to 4.92 μm, and the luminance is also implemented. It was inferior to Example 3. Further, since the film thickness is thick, the hardness, elastic deformation rate, residue, sensitivity, adhesion, developability, and shape are all inferior.

  Further, in Comparative Examples 7 and 8 using a combination of PG7 and PG36 as the green pigment, the film thickness is improved over PG36 in order to achieve the same chromaticity (x, y) as in Example 3. Although it was necessary to increase the thickness, the luminance was improved as compared with PG7, but it was inferior to Example 3. Moreover, since the film thickness was thick, the residue, developability, and shape were inferior.

E. Production of color filter (color filter example 1)
(1) Formation of black matrix A photosensitive black resin CK-2000 (trade name, manufactured by Fuji Hunt Technology Co., Ltd.) is spin coated on a 1.1 mm thick glass substrate (AL material manufactured by Asahi Glass Co., Ltd.). It was applied and dried at 100 ° C. for 3 minutes to form a light shielding layer having a thickness of 1.0 μm. The light-shielding layer is exposed to a light-shielding pattern with an ultra-high pressure mercury lamp, developed with a 0.5 wt% potassium hydroxide aqueous solution, and then subjected to heat treatment by leaving the substrate in an atmosphere at 230 ° C. for 30 minutes. Thus, a black matrix was formed in the region where the light shielding portion was to be formed.

(2) Formation of colored layer On the substrate on which the black matrix has been formed as described above, the photosensitive red composition CR-2000 (trade name, manufactured by Fuji Hunt Technology Co., Ltd.) was applied by spin coating (coating thickness). 2.0 μm) and then dried in an oven at 70 ° C. for 30 minutes.
Next, a photomask is placed at a distance of 100 μm from the coating film of the photosensitive red composition, and ultraviolet rays are applied only to the region corresponding to the colored layer forming region using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Irradiated for 2 seconds. Subsequently, it was immersed in a 0.5 wt% potassium hydroxide aqueous solution (liquid temperature 23 ° C.) for 1 minute and alkali-developed to remove only the uncured portion of the coating film. Thereafter, the substrate was left to stand in an atmosphere of 230 ° C. for 30 minutes to perform a heat treatment to form a red relief pattern in a region where a red pixel was to be formed.

Next, using the photosensitive green composition A, a green relief pattern was formed in an area where a green pixel was to be formed, in the same process as the red relief pattern formation.
Furthermore, using the photosensitive blue resin composition CB-2000 (trade name, manufactured by Fuji Hunt Technology Co., Ltd.), a blue relief pattern is formed in a region where a blue pixel is to be formed in the same process as the red relief pattern formation. A colored layer composed of three colors of red (R), green (G), and blue (B) was formed to obtain a color filter.

(3) Formation of protective film A clear resist (trade name Optmer SS6917, manufactured by JSR Corporation) is applied onto a glass substrate on which a colored layer has been formed, and dried to form a coating film having a dry film thickness of 2 μm. did. A photomask was placed at a distance of 100 μm from this coating film, and ultraviolet rays were irradiated for 10 seconds only to the region corresponding to the colored layer forming region using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Subsequently, it was immersed in a 0.5 wt% potassium hydroxide aqueous solution (liquid temperature 23 ° C.) for 1 minute and alkali-developed to remove only the uncured portion of the coating film. Thereafter, the substrate was left in an atmosphere of 200 ° C. for 30 minutes to perform a heat treatment to form a protective film, thereby obtaining a color filter having a colored layer and a protective film.

(4) Formation of spacer On a glass substrate on which a colored layer has been formed, a column resist having the following composition (product name Color Mosaic, product number CK-2000, manufactured by Fuji Film Ohlin Co., Ltd.) is applied by a spin coating method and dried. A coating film having a dry film thickness of 5 μm was formed. A photomask was placed at a distance of 100 μm from this coating film, and ultraviolet rays were irradiated for 10 seconds only on the spacer formation region on the black matrix using a 2.0 kW ultrahigh pressure mercury lamp by a proximity aligner. Next, it was immersed in a 0.5 wt% aqueous potassium hydroxide solution (liquid temperature 23 ° C.) for 1 minute and alkali-developed to remove only the uncured portion. Thereafter, the substrate was left to stand in an atmosphere at 230 ° C. for 30 minutes to perform heat treatment to form a fixed spacer, and a color filter having a colored layer and a spacer was obtained. The obtained color filter was a color filter having a wide color reproduction range and high brightness.

E. Production of Liquid Crystal Panel A transparent electrode film was formed on the surface including the fixed spacer of the color filter obtained in the above example using a discharge temperature of argon and oxygen at a substrate temperature of 200 ° C., and ITO as a target by DC magnetron sputtering. Thereafter, an alignment film made of polyimide was further formed on the transparent electrode film.

Next, the color filter and the glass substrate on which the TFT is formed are bonded by using an epoxy resin as a sealing material and applying a pressure of 0.3 kg / cm ² at 150 ° C., and a TN liquid crystal is sealed. Thus, the liquid crystal panel of the present invention was produced.

It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel. It is a figure which shows the xy chromaticity coordinate area | region (area | region A and area | region C) which can express a 1st green pigment and a 2nd green pigment in the XYZ color system of CIE. It is a figure which shows area | region A, B, and C on an xy chromaticity coordinate area | region. It is a figure which shows the monochromatic spectral transmittance spectrum of a 1st green pigment, a 2nd green pigment, and the conventional green pigment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Liquid crystal drive side board | substrate 3 ... Gap part 4 ... Sealing material 5 ... Transparent substrate 6 ... Black matrix layer 7 (7R, 7G, 7B) ... Pixel part 8 ... Protective film 9 ... Transparent electrode film 10 ... Orientation Film 11 ... Particulate spacer 12 ... Columnar spacer

Claims (13)

CIE XYZ color system as a reactive component involved in the curing reaction, consisting of brominated zinc phthalocyanine containing less than 13 bromine on average in the molecule as the first green pigment, measured alone with an F10 light source 1 type selected from the green pigments for color filters capable of displaying the xy chromaticity coordinate region surrounded by the following equations 1, 2 and 3, and the average of 13 or more bromine in one molecule as the second green pigment It is composed of brominated zinc phthalocyanine , and is selected from green pigments for color filters that can display the xy chromaticity coordinate area surrounded by the following equations 4, 5 and 6 in the CIE XYZ color system when measured alone with an F10 light source. The photosensitive coloring composition for color filters containing the coloring component containing at least 1 type which is.
(Equation 1)
y = 2.640 × x + 0.080
However, in Equation 1, 0.180 <x <0.230
(Equation 2)
y = 5261.500 × x ⁴ −6338.700 × x ³ + 2870.400 × x ² −580.730 × x + 44.810
However, in Equation 2, 0.230 <x <0.350
(Equation 3)
y = −36.379 × x ³ + 37.410 × x ² −13.062 × x + 1.907
However, in Equation 3, 0.180 <x <0.350
(Equation 4)
y = 8.000 × x−1.513
However, in Equation 4, 0.260 <x <0.270
(Equation 5)
y = −1051.300 × x ⁴ + 1176.900 × x ³ −450.880 × x ² + 62.131 × x−0.836
However, in Equation 5, 0.260 <x <0.350
(Equation 6)
y = 5746.700 × x ⁴ −7310.300 × x ³ + 3493.200 × x ² −744.610 × x + 60.251
However, in Equation 6, 0.270 <x <0.350   The first green pigment has a wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum, and is 500 to 520 nm, and the second green pigment has a spectral transmittance spectrum at 380 to 780 nm. The photosensitive coloring composition for color filters of Claim 1 whose wavelength (Tmax) from which the transmittance | permeability of this is the maximum is 520-535 nm. The photosensitive coloring composition for color filters of Claim 1 or 2 whose average primary particle diameter of the said brominated zinc phthalocyanine is 0.01-0.1 micrometer. The color filter photosensitivity according to any one of claims 1 to 3 , wherein a mass ratio (b / a) of a non-reactive component (b) other than the coloring component to the reactive component (a) is 0.45 or less. Coloring composition. The photosensitive coloring composition for color filters according to any one of claims 1 to 4 , wherein the pigment / vehicle ratio is 0.25 to 1.0. The photosensitive coloring composition for color filters according to any one of claims 1 to 5 , comprising at least one or more yellow pigments as the coloring component together with the first and second green pigments. The green pigment and the yellow pigment containing the first and second green pigments are contained at a ratio in which the mass ratio of the yellow pigment to the green pigment (yellow pigment / green pigment) is 1.6 or less. The photosensitive coloring composition for color filters according to claim 6 . A color filter comprising a green pixel formed using the photosensitive coloring composition for a color filter according to any one of claims 1 to 7 . The green pixel has a film thickness of 2.5 μm or less, and the x coordinate in the XYZ color system of CIE when the color is measured with an F10 light source with a single pixel is 0.25 ≦ x ≦ 0.32, y The color filter according to claim 8 , wherein a color space having coordinates of 0.55 ≦ y ≦ 0.75 and a stimulus value Y of 30 ≦ Y can be displayed. The green pixel contains a green pigment and a yellow pigment containing the first and second green pigments in a ratio such that a mass ratio of the yellow pigment to the green pigment (yellow pigment / green pigment) is 1.6 or less. In the CIE XYZ color system, when the color is measured with a F10 light source with a single pixel, the x coordinate is in the range of 0.25 ≦ x ≦ 0.32, and the y coordinate is in the range of 0.55 ≦ y ≦ 0.75. The color filter according to claim 8 , wherein a degree coordinate area can be displayed. 11. The color filter according to claim 8 , wherein the green pixel has a hardness of 500 N / mm ² or more and an elastic deformation rate of 20% or more. The color filter according to any one of claims 8 to 11 , wherein a ratio of the length of the upper base to the length of the lower base of the cross section of the green pixel is less than one. A liquid crystal panel comprising the color filter according to any one of claims 8 to 12 and a liquid crystal driving side substrate facing each other, and liquid crystal sealed between them.

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