JP4368157B2 - Green pigment for color filter, green pigment dispersion, photosensitive coloring composition, color filter, and liquid crystal panel - Google Patents

Description

  The present invention relates to a green pigment for a color filter, a pigment dispersion for a color filter and a photosensitive resin composition containing the green pigment, a color filter using them, 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 this 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 high luminance in a wide color gamut, 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 reproduction range 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 has high transmittance and high brightness, but has a low coloring power as green, so it is necessary to mix with PG7 to supplement the coloring power as green. When PG7 and PG36 are mixed, if the amount of PG7 is large, the total amount of pigment is small, but the transmittance is low. If PG36 is increased in order to increase the transmittance, the total amount of pigment increases. Accordingly, there has been a demand for pigments that can be used as main pigments in place of conventional copper halide phthalocyanine pigments such as PG7 and PG36.

  Generally, when the pigment blending ratio in the photosensitive coloring composition (photosensitive coloring resist) increases, the transparency of the pixel decreases and the luminance is difficult to increase. 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, in order to form a color filter with a wide color reproduction range and high luminance, a green pigment having excellent coloring power and high transmittance is required. However, a green pigment that sufficiently satisfies the requirement is still known. Absent.

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 the first object thereof is to display chromaticity coordinates that cannot be displayed with a conventional green pigment, and is excellent in coloring power as green and is too bluish. And providing a green pigment for a color filter having a high transmittance.

  In addition, the second object of the present invention is to provide a photosensitive coloring composition that uses the above-mentioned green pigment and has a high blending ratio of the photosensitive component, a sufficient color can be obtained with a relatively small amount of pigment, and is excellent in plate making. To provide things.

  A third object of the present invention is to provide a photosensitive coloring composition that uses the above green pigment to obtain a sufficient color even though the P / V ratio is low.

  In addition, a fourth object of the present invention is to provide a photosensitive coloring composition that can form a green pixel having a sufficiently strong yellowish green coloring property even when the amount of the yellow pigment is small. It is to provide.

  A fifth object of the present invention is to provide a photosensitive coloring composition that can form a color filter having a wide color reproduction range and high luminance by using the green pigment.

  The sixth object of the present invention is to provide a pigment dispersion suitable for preparing the photosensitive coloring composition using the green pigment.

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

The green pigment according to the present invention is composed of partially brominated zinc phthalocyanine containing an average of less than 13 bromines in one molecule, and in the XYZ color system of CIE when measured alone with an F10 light source, The xy chromaticity coordinate region surrounded by 3 can be displayed.
(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

The partially brominated zinc phthalocyanine preferably has a wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum is 500 to 520 nm.

  The green pigment made of partially brominated zinc phthalocyanine can display the xy chromaticity coordinate region surrounded by the above-mentioned equations 1, 2, and 3, and is preferably used as the green pigment of the present invention.

  The green pigment according to the present invention can display the xy chromaticity coordinate area surrounded by the above equations 1, 2, and 3 in the CIE XYZ color system when the green pigment alone is coated. The green color of the chromaticity coordinate region, which could not be displayed with the green pigment, is developed, and the color reproduction region can be expanded as compared with the case of using the conventional green pigment. In addition, since the green pigment of the present invention is excellent in coloring power, it can be close to the green color specified in the standard with a small amount compared to the case of using a conventional partially brominated copper phthalocyanine pigment (PG36). The plate-making property is improved, and a fine shape can be easily formed by photolithography. In addition, since the green pigment of the present invention has a high transmittance, when forming a color filter using the green pigment of the present invention, the light of the color filter is compared with the case of using a chlorinated copper phthalocyanine pigment (PG7). Therefore, a strong backlight is not necessary, and an increase in cost of the liquid crystal panel and an increase in power consumption can be suppressed.

  Before preparing the photosensitive coloring composition, the green pigment of the present invention may be prepared in advance in a pigment dispersion, and the resulting pigment dispersion and the photosensitive component may be mixed. When a partially brominated zinc phthalocyanine green pigment having an average primary particle size of 0.01 to 0.1 μm is used as the green pigment of the present invention, the dispersibility in a colored resin or the like is particularly good.

  The photosensitive coloring composition for a color filter according to the present invention contains a reactive component involved in a curing reaction, one or more coloring components including the green pigment of the present invention, and a non-reactive component other than the coloring component. 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.

  Since the photosensitive coloring composition can provide sufficient color developability with a small amount of pigment, the amount of the pigment and the dispersant used for dispersing the pigment can be reduced, and the amount of the reactive component can be relatively increased. it can. 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.

  The photosensitive coloring composition preferably uses the green pigment for color filter according to the present invention as a main pigment in order to obtain sufficient color developability with a small amount of pigment, and the color filter according to the present invention in the coloring component. It is preferable to contain more than 30% by mass of the green pigment for use. Moreover, it is preferable that the color filter green pigment is contained in an amount of 50% by mass or more based on the total amount of the green pigment in the coloring component.

  Moreover, in order to form a green pixel, the said photosensitive coloring composition can be made to contain a yellow pigment at least with a green pigment. In this case, since sufficient color developability can be obtained even under a small amount of yellow pigment such that the mass ratio of the yellow pigment to the green pigment containing the green pigment of the present invention (yellow pigment / green pigment) is 1.6 or less, the yellow pigment The amount of use can also be reduced.

The color filter according to the present invention is provided with a green pixel containing the green pigment of the present invention. This green pixel can be created using the photosensitive coloring composition of the present invention.
The green pixel has a film thickness of 2.7 μm or less, and when a single pixel is used for color measurement with an F10 light source, the x coordinate is 0.21 ≦ x ≦ 0.30 and the y coordinate is 0 in the CIE XYZ color system. A color space in which .55 ≦ y ≦ 0.71 and the stimulus value Y is in the range of 29 ≦ 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 yellow by simply mixing a small amount of yellow pigment, and the mass ratio of the yellow pigment to the green pigment containing the green pigment of the present invention in the pixel (yellow pigment / green (Pigment) is 1.6 or less, the x-coordinate is 0.21 ≦ x ≦ 0.30 and the y-coordinate is 0.55 ≦ y in the CIE XYZ color system when the color is measured with an F10 light source with a single pixel. An xy chromaticity coordinate region in a range of ≦ 0.71 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. Using the color filter and the liquid crystal panel of the present invention, an area having a high coloring power (high density area) such as a display standard for a multimedia monitor such as sRGB or a display standard for a color television such as NTSC or EBU. It is possible to manufacture a liquid crystal display device that can satisfy the above requirements.

  As described above, the green pigment according to the present invention can display color coordinates that cannot be displayed by the conventional green pigment, has excellent coloring power as green, is not too bluish, and has a high transmittance. It is preferably used to form a green pixel. Since the green pigment according to the present invention can produce sufficient color with a relatively small amount of pigment, the amount of the pigment itself used can be reduced, and the yellow pigment mixed for toning or the strong yellowish green Since the amount of the pigment used can be reduced, a green pixel which is thin and highly transparent and excellent in color purity can be formed. Moreover, since many yellow pigments are inferior in heat resistance and light resistance, the use amount of the yellow pigment is reduced, so that the resistance of the green pixel is also improved.

  Furthermore, the total amount of the green pigment and the yellow pigment or the strong yellowish green pigment of the present invention is reduced, and as a result, the amount of the dispersant used in the pigment dispersion and the photosensitive coloring composition is also reduced. Thus, a green pixel having excellent physical properties such as hardness, elasticity, shape, and film thickness uniformity can be obtained.

  Since such a green pixel using the green pigment according to the present invention has a wide color reproduction region, high brightness, and excellent physical properties, the color filter having such a green pixel has high display performance. In addition, by using a liquid crystal panel, it is possible to satisfy a region (high density region) having high coloring power such as a display standard for multimedia monitors such as sRGB or a color television display standard such as NTSC or EBU. A 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 green pigment for a color filter provided by the present invention is composed of a phthalocyanine green pigment, and the xy chromaticity coordinates surrounded by the following equations 1, 2, and 3 in the CIE XYZ color system when measured alone with an F10 light source. An area (hereinafter, sometimes referred to as “area A”) can be displayed. An xy chromaticity coordinate region (region A) surrounded by equations 1, 2, and 3 is shown in FIG.
(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

  The following equation is a display in the XYZ color system of CIE 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).

Among the xy chromaticity coordinate areas (area A) surrounded by equations 1, 2, and 3, the xy colors surrounded by the following equations 4, 5, and 6 in the CIE XYZ color system when measured alone with the F10 light source A green pigment capable of displaying a degree coordinate region (hereinafter, sometimes referred to as “region B”) does not have too much bluish color and does not reduce luminance, and does not have too much yellowish color and reduces the coloring power as green. It is particularly preferable because there is no problem. An xy chromaticity coordinate region (region B) surrounded by the following equations 4, 5 and 6 is shown in FIG.
(Equation 4)
y = 4.000 × x−0.270
However, in Equation 4, 0.210 <x <0.220
(Equation 5)
y = 3849.200 × x ⁴ −4595.600 × x ³ + 2056.300 × x ² −409.710 × x + 31.138
However, in Equation 5, 0.220 <x <0.350
(Equation 6)
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 6, 0.210 <x <0.350

  The phthalocyanine green pigment used in the present invention is 380 to 380 when the wavelength (Tmin) at which the transmittance of the spectral transmittance spectrum is minimized is 5% from the point that the xy chromaticity coordinate region in the above range can be displayed. The wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 780 nm is maximized 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 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 45% or less, particularly 40% or less. It is preferable that the transmittance of the spectral transmittance spectrum at 610 nm, which is the wavelength of the red light source, is 20% or less, particularly 10% or less. The spectral transmittance spectrum can be measured using a microspectrophotometer (for example, OSP-SP200 microspectrophotometer manufactured by Olympus Corporation).

  Examples of the central metal of the phthalocyanine green pigment used in the present invention include Zn, Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Ge, and Sn. Among them, the transmittance is high, Zn (zinc) is preferable because the xy chromaticity coordinate region in the above range can be displayed. Zinc is particularly suitable for displaying the NTSC, EBU standard green color 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 partially brominated zinc phthalocyanine in which at least one hydrogen atom is substituted with a bromine atom can display the xy chromaticity coordinate region surrounded by the above equations 1, 2, and 3, and It is preferably used as a green pigment for a color filter of the present invention. Among the partially brominated zinc phthalocyanines, partially brominated zinc phthalocyanines having an average of 8 to less than 13 bromine atoms in one molecule have good coloring power as green, are not too bluish, and have high transmittance. It is very suitable for coloring green and forming green pixels of color filters. Among these, partially brominated zinc phthalocyanine having an average of 10 to 11 bromine atoms in one molecule is preferable.

  Such a partially 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 partially 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 completion of the reaction, the produced partially brominated zinc phthalocyanine is precipitated. Thereafter, post-treatment such as filtration, washing, and drying is performed to obtain partially brominated zinc phthalocyanine.

  Then, this partially 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 the solvent salt milling method or the solvent boiling method. As a result, a partially brominated zinc phthalocyanine pigment that is excellent in dispersibility and coloring power and that develops a green color with high brightness can be obtained. There is no particular limitation on the pigmentation method, and partial bromination zinc phthalocyanine may be dispersed in a dispersion medium and pigmentation may be performed at the same time, but from a solvent treatment where the partial bromination zinc phthalocyanine is heated and stirred in a large amount of organic solvent. However, 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 a partially brominated zinc phthalocyanine that is 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 partially 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 partially 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 partially 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. Etc. 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 partially brominated zinc phthalocyanine pigment, an inorganic salt, and an organic solvent as a main component is obtained. The organic solvent and the inorganic salt are removed from this mixture, and a partially brominated zinc phthalocyanine pigment is used as necessary. A partially brominated zinc phthalocyanine pigment powder can be obtained by washing, filtering, drying, pulverizing, etc. a solid mainly composed of. 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 partially brominated zinc phthalocyanine pigment having an average primary particle size of 0.01 to 0.1 μm is obtained.

  Any of the green pigments of the present invention represented by this partially brominated zinc phthalocyanine pigment can be used for known and commonly used applications. Particularly, pigments having an average primary particle size of 0.01 to 0.1 μm should be colored. Dispersibility in a synthetic resin or the like becomes better. The partially 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, when used in a color filter, pigment aggregation is relatively weak especially when the average particle size of the primary particles is in the range of 0.01 to 0.1 μm, and the pigment dispersion into the color filter resist ink is easy. In addition, a color filter having both high definition and brightness can be obtained more easily, and the light-shielding property at 365 nm, which is frequently used when curing resist inks for color filters, is reduced, and the photocuring sensitivity of the resist. This is preferable because the film edge and pattern flow hardly occur during development.

  When the aspect ratio of the primary particles is 1 to 3, the green pigment of the present invention has 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 green pigment according to the present invention 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 is coated alone, It produces a green color that cannot be displayed with a conventional green pigment that has high strength and is not too bluish and has a high transmittance, and the color reproduction range can be expanded as compared with the case of using a conventional green pigment. As a result, the green pigment according to the present invention is a pigment that combines the advantages of the conventional chlorinated copper phthalocyanine pigment (PG7) and the partially brominated copper phthalocyanine pigment (PG36). In addition, since the green pigment of the present invention is excellent in coloring power, it can be close to the standard green color with a small amount compared to the case of using the conventional PG36, so that the film thickness can be reduced, and the photo Lithography improves platemaking and facilitates the formation of fine shapes. Further, since the green pigment of the present invention has a high transmittance, when the color filter is formed using the green pigment of the present invention, the light transmittance of the color filter is increased as compared with the case of using PG7. This eliminates the need for a strong backlight, and can suppress an increase in cost and power consumption of the liquid crystal panel. Since the green pigment according to the present invention develops a green color with a relatively strong bluish color, it is particularly suitable for the NTSC and EBU standards for televisions that require a green pixel with a relatively strong bluish color.

  Further, when the green pigment according to the present invention comprises a partially brominated zinc phthalocyanine pigment, the transmittance is high, and the transmittance of the spectral transmittance spectrum at a wavelength of 435 nm is 45% or less, particularly 40% or less, A pigment with less extra bluish color that must be removed by toning is obtained. Further, the transmittance of the spectral transmittance spectrum at 610 nm is 20% or less, particularly 10% or less, and a pigment with less redness is obtained even when toning.

  In order to measure the color of the green pigment according to the present invention as a single unit, an appropriate dispersant, binder component and solvent are blended with the green pigment to prepare a coating solution, which is coated on a transparent substrate. And may be dried and cured as necessary. 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 colored resin composition of the present invention described later, a coating film containing only the green pigment according to the present invention is formed as the pigment, and colorimetry is performed. You can also.

  A green pixel of a color filter can be formed by a known method using the green pigment of the present invention. As a method for producing a green pixel, for example, a green pigment according to the present invention is mixed with a photosensitive component such as a photopolymerizable compound or a photopolymerization initiator to prepare a photosensitive coloring composition, which is used as a transparent substrate. A green pixel can be formed by applying on top, exposing to a predetermined pattern and developing. In addition, a color filter may be manufactured by forming a green pattern by an electrodeposition method, a transfer method, a micelle electrolysis method, or a PVED (Photovoltaic Electrodeposition) method. In addition, a red pattern and a blue pattern can also be formed by a similar method using a known pigment.

  Before preparing the photosensitive coloring composition, a green pigment may be prepared in advance in a pigment dispersion, and the obtained pigment dispersion and the photosensitive component may be mixed. In this case, a photosensitive coloring composition having good pigment dispersibility can be obtained.

  The green pigment for a color filter of the present invention can be used alone as a coloring component, but is usually prepared in combination with other pigments such as a yellow pigment at the stage of preparing a pigment dispersion or a photosensitive coloring composition. To be colored. The green pigment for a color filter of the present invention is excellent in coloring power as green, is not too bluish, and has a high transmittance. Therefore, the main pigment in the coloring component in the pigment dispersion for color filter or the photosensitive coloring composition Furthermore, it can be suitably used as the main pigment of the green pigment in the coloring component. The green pigment of the present invention is more than 30% by mass and further 39% by mass based on the total amount of coloring components in the photosensitive coloring composition in terms of forming a green pixel of a color filter having a wide color reproduction range and a high luminance. As mentioned above, it is preferable that more than 50 mass% is contained especially.

  Moreover, it is preferable that the green pigment of this invention is contained 50 mass% or more based on the whole quantity of the green pigment in the coloring component in a photosensitive coloring composition, and also 60 mass% or more. Furthermore, depending on the target color coordinates, there may be a case where the amount of the other green pigment added is extremely small, and the amount of the green pigment of the present invention is 80% by mass or more based on the total amount of the green pigment. Even if it is 100 mass%, it is possible to adjust to the target color coordinate.

  When preparing a pigment dispersion or a photosensitive coloring composition, with a relatively small amount of pigment used, it approaches the color of each standard green pixel, increases the brightness, thins the film thickness, and widens the color reproduction range. From the above, at least one kind selected from the green pigments for color filters according to the present invention as the first green pigment in the coloring component, and green having a yellowish color stronger than the first green pigment as the second green pigment A pigment may be contained.

  The first green pigment is selected from the green pigments for color filters according to the present invention. Among them, the green pigment capable of displaying the region B is not too strong blue and does not lower the luminance. In particular, the yellowishness is not too strong, and the coloring power as green is not lowered, which is particularly preferable.

  The second green pigment having a yellowish color stronger than the first green pigment has a wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum, which is longer than that of the first green pigment. However, 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, preferably 0.02. It is preferable that the distance is ˜0.05 away from the point that it is close to the color of each standard green pixel with a relatively small amount of pigment used and the effect of widening the color reproduction range is high. If the above-described conditions are satisfied, the second green pigment may be selected from the green pigments for color filters according to the present invention, or when a wide color gamut or a green pixel with a strong yellow is required. The green pigment for the color filter of the present invention may be selected from green pigments having a stronger yellowness.

  In this case, the green pigment having a yellowish color stronger than the green pigment for a color filter of the present invention does not display the xy chromaticity coordinate region surrounded by the above equations 1, 2, and 3, and is at 380 to 780 nm. The wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum is maximized is preferably greater than 515 nm and not greater than 535 nm.

  The coloring component may further contain a plurality of pigments as a green pigment, such as a third green pigment and a fourth green pigment. Even in that case, it is preferable that the first green pigment and the second green pigment are separated from each other on the xy chromaticity coordinate region in terms of increasing the effect of expanding the color reproduction range. When x is fixed at y = 0.50 on the xy chromaticity coordinates, each x is preferably 0.02 or more, preferably 0.03 to 0.05.

  Further, by combining the green pigment of the present invention with a yellow pigment, 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.

  The green pigment of the present invention has a low spectral transmittance spectrum at a wavelength of 380 to 470 nm as compared with conventional green pigments, and has a relatively large amount of yellowish component while being sufficiently colored as green. When forming green pixels, the amount of yellow pigment used can be reduced. When preparing a pigment dispersion or a photosensitive coloring composition by mixing a green pigment and a yellow pigment, the total amount of the green pigment containing the green pigment of the present invention, and optionally including the second or more green pigments. Even when the mixing ratio of the yellow pigment is preferably 1.6 or less, more preferably 0.8 or less in terms of mass ratio (yellow pigment / green pigment), the transmittance of the spectral transmittance spectrum at a wavelength of 380 to 470 nm is sufficient. Can be reduced. Furthermore, when combined with the green pigment of the present invention, a highly transparent yellow pigment can be used as a yellow pigment, and thus a more transparent green pixel can be obtained.

  Since the green pigment according to the present invention has excellent coloring power and high transmittance, sufficient color development can be obtained even with a small amount of the green pigment itself. The amount can be reduced, the amount of the entire pigment used is reduced, and a green pixel having high transparency and excellent color purity can be formed. In addition, since many yellow pigments are inferior in heat resistance and light resistance, the resistance of green pixels is improved by reducing the amount of yellow pigment used.

  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, when the green pigment of the present invention is used, it is possible to obtain 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 pigment contained in the photosensitive coloring composition, and includes other pigments such as a yellow pigment mixed with the green pigment. 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.

  In addition, as the amount of pigment used decreases, the amount of dispersant used to disperse the pigment can also be reduced, so components that do not participate in the curing reaction such as pigments and dispersants (non-reactive components), light When a pixel is formed using a photosensitive coloring composition comprising a component (reactive component) involved in a curing reaction such as a curable resin, an initiator, or a thermosetting resin, the blending ratio of the non-reactive component is It decreases, and the proportion 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.

  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 Chemicals), Florard Fc430, Fc431 (Sumitomo 3M), Solsperse 13240, 20000, 24000, 26000, 28000, etc. ), Dispersic 111, 161, 162, 163, 164, 182, 2000, 2001 (produced by Big Chemie), Addisper PB711, PB411, PB111, PB821, PB822 (produced by Ajinomoto Fine Techno) and 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 pigment (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 pigment (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 green pigment of the present invention may be prepared as a dispersion separately from other pigments, or may be prepared as a dispersion by mixing with other pigments.

  The photosensitive coloring composition contains a component involved in photocuring, such as a photopolymerizable compound and a photopolymerization initiator, together with a green pigment, other pigments and a dispersant, that is, a photosensitive component, and if necessary, a solvent. Prepared by appropriate dilution.

  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), DaroCure (manufactured by Merck), Adeka 1717 (manufactured by Asahi Denka Kogyo Co., Ltd.), 2 , 2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (manufactured by Kurokin Kasei Co., Ltd.) Can be mentioned. 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 a photosensitive coloring composition, the green pigment of the present invention, other pigments, a dispersant, a photopolymerizable compound, a photopolymerization initiator, and other components are added to an appropriate solvent, or the present invention. A pigment dispersion composed of a green pigment, other pigments, a dispersing agent, and the like, a photosensitive component such as a photopolymerizable compound and a photopolymerization initiator, and other components are put into a solvent, and a paint shaker, bead mill, sand What is necessary is just to melt | dissolve and disperse | distribute by general methods, such as a grind mill, an attritor mill, a 2 roll mill, a 3 roll mill, a 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 is exposed by applying a photosensitive coloring composition containing the green pigment of the present invention on one side of a transparent substrate and irradiating with light through a photomask. After alkali development, heat curing in a clean oven or the like Can be formed. 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 light irradiation through a photomask, and after alkali development, 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.

  As for the spacer on the transparent electrode, the coating solution of the photosensitive resin composition is applied by a method such as spin coater, roll coater, spray, printing, etc., exposed by light irradiation through a photomask, and after alkali development, a clean oven It can be formed by heat curing with, for example. 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 contains the green pigment of the present invention.

  The green pixel has a film thickness of 2.7 μm or less, preferably 2.5 μm or less, and when the color is measured with an F10 light source with a single pixel, the x coordinate is 0.21 ≦ x ≦ 0 in the CIE XYZ color system. .30, a color space in which the y coordinate is 0.55 ≦ y ≦ 0.71 and the stimulus value Y is 29 ≦ Y, more preferably 50 ≦ Y, can be displayed, and can be combined with other color pixels to achieve a wide color range. The reproduction area can be secured, and the brightness is very high even if the film thickness is small.

  The green pixel contains at least one kind selected from the green pigments for color filters as the first green pigment and a green pigment having a yellowish color stronger than the first green pigment as the second green pigment. In the XYZ color system of CIE when color measurement is performed with a single pixel using an F10 light source, the x coordinate is in the range of 0.21 ≦ x ≦ 0.30 and the y coordinate is in the range of 0.55 ≦ y ≦ 0.71. The chromaticity coordinate area can be displayed. Since a strong yellowish green color can be displayed, a wide color reproduction area can be ensured by combining with pixels of other colors.

  Further, the green pixel can be enhanced in yellowness only by mixing a small amount of yellow pigment, and the mass ratio of the yellow pigment to the green pigment containing the green pigment of the present invention in the pixel (yellow pigment / green (Pigment) is 1.6 or less, the x-coordinate is 0.21 ≦ x ≦ 0.30 and the y-coordinate is 0.55 ≦ y in the CIE XYZ color system when the color is measured with an F10 light source with a single pixel. An xy chromaticity coordinate region in a range of ≦ 0.71 can be displayed.

  In addition, the green pixel has less non-photosensitive 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. Since the blending ratio of developable components such as an alkali-soluble binder can be increased, the photocurability, the ability to form a fine pattern, and the physical properties after pixel formation are good, specifically, the irradiation sensitivity is good. Residue hardly occurs, no foreign matter remains, 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. Further, since the obtained pixel has a high cross-linking density, it is excellent in hardness and elasticity, and has 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 demand, a sufficient amount of the curing component can be used by using the green pigment of the present invention, so that a color filter with reduced impurity elution and excellent voltage holding ratio is produced. Applicable to.

  A liquid crystal panel can be 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 it. 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 according to the present invention has been described using a color filter for a liquid crystal display device as a representative example, the present invention can be applied to an active color filter regardless of the drive mode such as TN, IPS, and VA. Further, the present invention is not limited to the active method, and can be applied to various types of drive-type color filters, such as a simple matrix method. Furthermore, color filters for other types of display devices other than liquid crystal display devices, such as EL (electroluminescence). It can also be applied 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)
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride. 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 partially brominated zinc phthalocyanine crude pigment. The 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 partially brominated zinc phthalocyanine crude pigment.

  1 part by weight of this partially 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, the mixture was taken out into 100 parts by mass of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a partially brominated zinc phthalocyanine pigment (hereinafter referred to as pigment composition (1)).

The obtained partially brominated zinc phthalocyanine pigment has an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc: phthalocyanine) and contains an average of 10 bromines in one molecule, based on a halogen content analysis by mass spectrometry. It was.
The average primary particle size measured with a transmission electron microscope (JEM-2010, manufactured by JEOL Ltd.) was 0.065 μm.

(Synthesis Example 2)
Zinc phthalocyanine was produced from phthalodinitrile and zinc chloride. This 1-chloronaphthalene solution had light absorption at 600-700 nm. In 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 2.63 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 partially brominated zinc phthalocyanine crude pigment. This aqueous slurry was filtered, washed with hot water at 60 ° C., and dried at 90 ° C. to obtain 2.8 parts by mass of a purified partially brominated zinc phthalocyanine crude pigment.

  In this partially brominated zinc phthalocyanine crude pigment, other components were charged in the same composition as in Synthesis Example 1 above, and pigmented using the kneader in the same manner to obtain a partially brominated zinc phthalocyanine pigment (hereinafter referred to as pigment composition (2)). )

The obtained partially brominated zinc phthalocyanine pigment had an average composition of ZnPcBr ₁₂ Cl ₃ H (Pc; phthalocyanine) and contained an average of 12 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 Example 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 partially brominated zinc phthalocyanine pigment dispersion (1). did. 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 Example 2)
A partially brominated zinc phthalocyanine pigment dispersion (2) was prepared in the same manner as in the dispersion example 1, except that the pigment composition (2) synthesized in the synthesis example 2 was used instead of the pigment composition (1). Prepared and evaluated similarly to Dispersion Example 1. 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.

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

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

  In dispersion examples 1 and 2 according to 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 is reduced. It became clear that 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, in dispersion examples 1 and 2 according to the present invention, it was revealed that the chromaticity coordinate region between PG7 and PG36 can be displayed, and the Y value is relatively high, that is, the brightness is high.

  Further, in dispersion examples 1 and 2 according to the present invention, the viscosity was lower than that of PG7 and PG36, and the dispersibility was good. Furthermore, in the dispersion examples 1 and 2 according to the present invention, the average particle size (50% particle size) is smaller than that of PG7 and PG36, so that the dispersion is fine and the dispersibility is good. all right.

C. Preparation of photosensitive green composition (photosensitive green composition example 1)
(1) Preparation of Yellow Pigment Dispersion A PY83 pigment dispersion was prepared in the same manner as Dispersion Example 1 except that PY83 was used instead of the pigment composition (1).

(2) Preparation of photosensitive green composition A In order to prepare an alkali-soluble photoreactive polymer, 70 parts of MMA, 15 parts of BzMA, 15 parts of MAA, and 100 parts of PGMEA were placed in a flask, and 93 hours at 93 ° C. in a nitrogen atmosphere. Polymerized. The solid content concentration of this reaction solution was adjusted to 40.2% with PGMEA. The acid value of the obtained polymer was 104 mgKOH, and the weight average molecular weight Mw in terms of polystyrene was 24,700.

Next, partially brominated zinc phthalocyanine pigment dispersion (1), PY83 pigment dispersion, alkali-soluble photoreactive polymer, dipentaerythritol pentaacrylate (hereinafter referred to as DPPA), Irgacure 369 (trade name) and PGMEA Then, photosensitive green composition A was prepared by mixing, stirring and filtering at room temperature.
<Composition of photosensitive green composition A>
-Brominated zinc phthalocyanine pigment dispersion (1): 49.00 parts-PY83 pigment dispersion: 8.65 parts-Alkali-soluble photoreactive polymer: 6.31 parts-DPPA (manufactured by 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 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.

D. Formation of Green Pixel (Green Pixel Examples 1-2, Green Pixel Comparative Examples 1-4)
Green pixels were prepared using the photosensitive green compositions A to B of the examples and the photosensitive green compositions C to F of the comparative examples, and the following items were evaluated. The evaluation results are shown in Table 3.

(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 formed color filter pixel 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 3 shows the thickness of each cured film with color evaluation of x = 0.257 and y = 0.963. Each of the items was evaluated thereafter using a coating film and a cured film in which x = 0.257 and y = 0.963 in 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 ultra-high pressure mercury lamp is applied to each coating film in which the cured film has x = 0.257 and y = 0.663 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 0.5 mass% aqueous potassium hydroxide solution at 23 ° C. for 1 minute with a spin developing machine, 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. The following evaluation was performed about the obtained green pixel. The results are shown in Table 3.

<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.

  In Examples 1 and 2 using the green pigment according to the present invention, the film thickness is as thin as 2.49 and 2.61 μm, and the x coordinate in the XYZ color system of CIE when color measurement is performed with a single pixel is 0.257, y coordinate 0.693 was realizable, and stimulus value Y was 31.5, 29.5 and brightness was high. The example using the green pigment according to the present invention had a thin film thickness, and an excellent pixel was obtained in terms of hardness, elastic deformation rate, residue, sensitivity, adhesion, developability, and shape.

  On the other hand, Comparative Example 1 using PG7 as the green pigment needs to contain a large amount of yellow pigment / green pigment = 0.9 and yellow pigment in order to achieve the same chromaticity (x, y) as in the example. 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 2 using PG36 as the green pigment, in order to realize the same chromaticity (x, y) as in the example, the film thickness needs to be increased to 4.92 μm, and the luminance is also in the example. It was inferior to 1 and 2. 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 3 and 4 in which PG7 and PG36 are used in combination as the green pigment, the film thickness is improved compared to PG36 in order to achieve the same chromaticity (x, y) as in the example. 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, 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 heat treatment, thereby forming 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.

(Color filter example 2)
A color filter having a colored layer and a protective film and a colored layer in the same manner as in color filter example 1 except that the photosensitive green composition B was used instead of the photosensitive green composition A to form a green pixel. A color filter having spacers 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 xy chromaticity coordinate area | region (area | region A) which the green pigment concerning this invention can represent. It is a figure which shows the area | region A and the area | region B on an xy chromaticity coordinate area | region. It is a figure which shows the monochromatic spectral transmittance spectrum of the green pigment which concerns on this invention, 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 (16)

An xy chromaticity coordinate region that is composed of partially brominated zinc phthalocyanine containing an average of less than 13 bromine atoms in one molecule and is surrounded by the following equations 1, 2, and 3 in the CIE XYZ color system when measured alone. Green pigment for color filters that can be displayed.
(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 2. The green pigment for a color filter according to claim 1, wherein the partially brominated zinc phthalocyanine has a wavelength (Tmax) at which the transmittance of the spectral transmittance spectrum at 380 to 780 nm is maximum is 500 to 520 nm. A green pigment dispersion for a color filter, comprising the partially brominated zinc phthalocyanine according to claim 1 or 2 , wherein the average primary particle diameter is 0.01 to 0.1 µm. A reactive component involved in the curing reaction, one or two or more colored components including the green pigment for a color filter according to claim 1 or 2 , a non-reactive component other than the colored component, and the reactive component The photosensitive coloring composition for color filters whose mass ratio (b / a) of the said non-reactive component (b) other than the coloring component with respect to (a) is 0.45 or less. The photosensitive coloring composition for color filters of Claim 4 whose pigment / vehicle ratio is 0.25-1.0. The photosensitive coloring composition for color filters of Claim 4 or 5 which contains more than 30 mass% of said green pigments for color filters in the said coloring component. The photosensitive coloring composition for color filters in any one of Claims 4 thru | or 6 which contains 50 mass% or more of said green pigments for color filters on the basis of the whole quantity of the green pigment in the said coloring component. The photosensitive coloring composition for a color filter according to any one of claims 4 to 7 , wherein the coloring component contains at least one yellow pigment together with the green pigment for a color filter. The green pigment for a color filter and the yellow pigment are contained at a ratio in which a mass ratio of the yellow pigment to a green pigment containing the green pigment for the color filter (yellow pigment / green pigment) is 1.6 or less. The photosensitive coloring composition for color filters according to any one of claims 4 to 8 . A color filter comprising a green pixel containing one or more pigments including the green pigment for a color filter according to claim 1 or 2 . A color filter provided with a green pixel formed using the photosensitive coloring composition for a color filter according to any one of claims 4 to 8 . The green pixel has a film thickness of 2.7 μm or less, and an x coordinate is 0.21 ≦ x ≦ 0.30 in the XYZ color system of CIE when the color is measured with an F10 light source with a single pixel, y The color filter according to claim 10 or 11 , wherein a color space having coordinates in a range of 0.55≤y≤0.71 and a stimulus value Y in a range of 29≤Y can be displayed. The green pixel contains at least a yellow pigment together with the green pigment for the color filter at a ratio such that the mass ratio of the yellow pigment to the green pigment including the green pigment for the color filter (yellow pigment / green pigment) is 1.6 or less. When the color is measured with an F10 light source with a single pixel, the XY color in the CIE XYZ color system has an x coordinate in the range of 0.21 ≦ x ≦ 0.30 and a y coordinate in the range of 0.55 ≦ y ≦ 0.71. The color filter according to claim 10 or 11 , wherein a degree coordinate area can be displayed. 14. The color filter according to claim 10 , wherein the green pixel has a hardness of 500 N / mm ² or more or an elastic deformation rate of 20% or more. The color filter according to claim 10 , wherein a ratio of an upper base length to a lower base length of a cross section of the green pixel is less than one. 16. A liquid crystal panel comprising the color filter according to claim 10 and a liquid crystal driving side substrate facing each other, and liquid crystal sealed between them.

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