TW201704364A - Pigment particles, pigment dispersion, photosensitive colored composition, and color filter - Google Patents

Abstract

The present invention addresses the issue of providing: a diketo pyrrolo pyrrole-based pigment particles that have excellent thermal resistance and good color properties and are suitable for production of a color filter having a reduced thickness; a pigment dispersion including the pigment particles; a photosensitive colored composition; and a color filter. Provided are diketo pyrrolo pyrrole-based pigment particles containing a compound indicated by general formula (I) and having a crystallite size in the planar direction of no more than 140Å, said planar direction corresponding to the maximum peak in an X-ray diffraction pattern among 8 (±1 ±1 ±1) planes among crystal lattice planes calculated using an X-ray diffraction pattern. Also provided are a pigment dispersion including said pigment particles, a photosensitive colored composition, and a color filter. [In the general formula (I), X1 and X2 each independently indicate a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF3, an optionally substituted saturated or unsaturated alkyl group, or an optionally substituted aryl group].

Description

Pigment fine particles, pigment dispersion, photosensitive coloring composition, and color filter

The present invention relates to novel pigment microparticles and pigment dispersions, photosensitive coloring compositions and color filters using the same.

a color filter used for a liquid crystal display device and a solid-state image sensor, generally, a coloring composition in which a color material of a dye or a pigment is dissolved or dispersed in a solvent, and a colored composition such as a resin is applied to a glass substrate or a tantalum substrate. After waiting, after exposure. It is manufactured by the steps of hardening, development, heat hardening, and the like. Since the durability of the color filter is related to the life of the liquid crystal display device and the solid-state image sensor, the color material of the coloring composition is mainly used as a pigment dispersion method using a pigment excellent in heat resistance or solvent resistance. The pigment dispersion used herein mainly uses a non-aqueous pigment dispersion in which a pigment is dispersed in an organic solvent, and a characteristic of primary particle diameter, dispersed particle diameter, crystallinity, and the like of the pigment fine particles contained in the dispersion, and the color of the final product. The properties of the color characteristics, heat resistance, etc. of the filter are greatly affected.

In recent years, color filters used in liquid crystal display devices and solid-state image sensors have been required to be rich in color and power saving. In order to achieve their goals, the color characteristics of color filters are strongly required to be higher. Characteristics such as ratio, high brightness, high tinting strength, etc.

The organic pigment used for the coloring agent in the red filter section is generally an organic pigment excellent in light resistance and heat resistance such as a diketopyrrolopyrrole pigment, an anthraquinone pigment or a disazo pigment. Alternatively, the organic pigments which are commercially available have a large primary particle size and are not uniform, so they are used as they are and cannot achieve the color characteristics required for the color filter. Therefore, there are many attempts to review the miniaturization of these organic pigments.

In particular, diketopyrrolopyrrole pigments are excellent in organic pigments, and have been used in recent years. Among them, CIpigment red 254 and brominated diketopyrrolopyrrole, especially organic pigments with excellent color characteristics, are actively reviewed for fineness. (hereinafter also referred to as "microparticles").

For example, as disclosed in Patent Documents 1 and 2, an inorganic salt such as sodium chloride is used as a medium, and an organic pigment and an organic solvent are prepared by mixing, and the organic pigment is processed by a kneading machine to pulverize the organic pigment. The so-called reprecipitation method in which the organic pigment described in Patent Document 3, Patent Document 4, or Patent Document 5 is dissolved in a solvent of a good solvent and a weak solvent in which the organic pigment is dissolved in the good solvent to form pigment fine particles, or a combination such as a patent The refining method described in Document 6 and the method for refining the organic pigment by the salt polishing method.

Further, it is provided as described in Patent Document 7 that it can be placed close to the opposite direction. In the film fluid formed between at least one of the separation surfaces and the at least two processing surfaces that are relatively rotated, the pigment solution in which the organic pigment is dissolved and the precipitation of the organic pigment particles are precipitated. A method of producing microparticles of a dose.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-211970

Patent Document 2: Japanese Laid-Open Patent Publication No. 2014-177532

Patent Document 3: Japanese Patent Publication No. 2011-046846

Patent Document 4: Japanese Laid-Open Patent Publication No. 2011-137142

Patent Document 5: International Publication WO2011/024896 Brochure

Patent Document 6: JP-A-2015-102858

Patent Document 7: International Publication WO2011/096401 Brochure

Summary of invention

The organic pigment fine particles which are miniaturized by using the conventional techniques described above have a certain effect on the performance of color filters such as high contrast and high brightness. However, according to the review by the inventors of the present invention, the high-contrast and high-brightness required for the color filter can not be sufficiently achieved by the prior art, and the patent document 3 or the patent document 5 is added. Since the materials other than the materials, etc., it is impossible to obtain the organic pigment fine particles and the dispersion thereof which can obtain the high contrast and high coloring power filter which has been strongly demanded in recent years.

The problem to be solved by the present invention is to provide a high contrast and high-brightness diketopyrrolopyrrole pigment microparticle, and in the case of using a pigment dispersion containing the pigment microparticle, a good filter segment is formed and has necessary properties, and A photosensitive coloring composition excellent in balance of properties, and a color-rich color filter excellent in brightness and excellent in contrast.

As a result of intensive studies by the present inventors, it has been confirmed that the diketopyrrolopyrrole pigment has crystal growth mainly in three directions, and it has been found that the crystallite size in a specific crystal growth direction is a certain value or less, or relative to each crystal growth direction. The diketopyrrolopyrrole pigment having a specific crystallite size ratio within a certain range has a fine and uniform primary particle diameter, and has a high level and a good balance to satisfy the above-described characteristics required as a color filter.

The present invention solves the problems by the following means.

(1) A diketopyrrolopyrrole pigment microparticle containing 90% or more of a compound represented by the following general formula (I), which is calculated by a X-ray diffraction pattern in a lattice plane (±1 ± Among the 8 faces of 1 ± 1), the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less. [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent].

(2) A diketopyrrolopyrrole pigment microparticle containing a compound represented by the following general formula (I), which is calculated by a X-ray diffraction pattern (±1 ± 1 ± 1) Among the eight faces, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less, and the (1 5 -1) plane direction is calculated by the X-ray diffraction pattern. The crystal size is below 80Å.

(3) A diketopyrrolopyrrole-based pigment microparticle containing a compound represented by the following general formula (I), which is an 8-sided surface of (±1 ± 1 ± 1) calculated by an X-ray diffraction pattern Among them, the crystallite size in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is divided by the lattice plane calculated by the X-ray diffraction pattern, and 2θ=3~10° The maximum peak corresponds to the crystallite size in the direction of the surface, and the ratio of the calculated crystallite size is 0.85 to 1.25, and the average primary particle diameter is 5 to 40 nm.

(4) A diketopyrrolopyrrole pigment fine particle containing 90% or more of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern and corresponds to 2θ = 24.5 ° ± 0.3 ° Crystallite size It is below 140Å.

(5) A diketopyrrolopyrrole pigment fine particle containing 90% or more of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern and corresponds to 2θ = 24.5 ° ± 0.3 ° The crystallite size of the crystal lattice is 140 Å or less, and the crystallite size corresponding to 2θ=28.0°±0.3° calculated by the X-ray diffraction pattern is less than 80 Å.

(6) The diketopyrrolopyrrole pigment fine particles according to the above item (1), (2), (4) or (5), wherein the average primary particle diameter is 5 to 40 nm.

(7) A diketopyrrolopyrrole pigment fine particle containing a compound represented by the following general formula (I), which is a crystal lattice corresponding to 2θ = 24.5 ° ± 0.3 ° calculated by an X-ray diffraction pattern The crystallite size of the surface is divided by the crystallite size of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern, and the ratio of the crystallite size calculated is 0.85 to 1.25, and the average The primary particle size is 5 to 40 nm.

(8) The diketopyrrolopyrrole pigment microparticles according to any one of the above items (1) to (7), wherein the maximum peak of 2θ=3 to 10° is calculated by the X-ray diffraction pattern The value of the surface spacing of the corresponding lattice surface at 80 ° C and the rate of change at 230 ° C (according to the following specific formula) are 3.0% or less, the value at 80 ° C and the value at 230 ° C. Rate of change = {(interval at 230 °C) / (interval at 80 °C) × 100} - 100 (%) [specific formula].

(9) A diketopyrrole according to any one of the above items (1) to (7) Pyrrole-based pigment microparticles, wherein the value of the interplanar spacing of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern is 80 ° C and the rate of change at 230 ° C ( The specific formula according to the following formula is 3.0% or less, and the rate of change at 80 ° C and the value at 230 ° C = {(interval at 230 ° C) / (interval at 80 ° C) × 100 }-100(%) [Specific formula].

(10) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (9), wherein the standard deviation of the primary particle diameter is less than 7.0.

(11) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (10), wherein a coefficient of variation (CV value) of the primary particle diameter is less than 30.

(12) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (11), wherein the content of Fe is 35 ppm or less.

(13) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (12), wherein the general formula (I) is represented by the following general formula (II), [In the above general formula (II), R is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkyl group which may have a substituent, or An aryl group which may have a substituent].

(14) The ketopyrrolopyrrole pigment microparticles of the above item (13), wherein R is bromine represented by the following formula (III),

(15) A diketopyrrolopyrrole-based pigment microparticle containing a compound represented by the following formula (III), which is (±1 ± 1 ± 1) in a lattice plane calculated by an X-ray diffraction pattern Among the eight faces, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less.

(16) A pigment dispersion which is a pigment dispersion containing at least an organic pigment and an organic solvent, wherein the organic pigment is a diketopyrrolopyrrole pigment according to any one of the above items (1) to (15) Microparticles.

(17) A photosensitive coloring composition containing at least the diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (15).

(18) A color filter comprising at least the photosensitive coloring composition of the above item (17).

(19) A color filter comprising at least the diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (15).

According to the present invention, the diketopyrrolopyrrole pigment fine particles having the characteristics of any one of the above (1) to (15), the pigment dispersion containing the pigment fine particles, the photosensitive coloring composition, and the color can be provided. Filter. By using the fine particles of the pigment, it is easy to disperse, and when a pigment dispersion containing the fine particles of the pigment is used, it can provide high contrast, high coloring power, and excellent heat resistance, and is useful as a color filter. A photosensitive coloring composition having suitable properties and a color filter excellent in contrast using the photosensitive coloring composition.

Fig. 1 is a schematic cross-sectional view showing a fluid processing apparatus for carrying out a fluid processing method according to an embodiment of the present invention.

[ Fig. 2] (A) is a schematic plan view of a first processing surface of the fluid processing apparatus shown in Fig. 1, and (B) is an enlarged view of a main part of a processing surface of the same apparatus.

[Fig. 3] (A) is a cross-sectional view of a second introduction portion of the same device, and (B) is an enlarged view of a main portion of the processing surface for description of the second introduction portion.

[Fig. 4] is an X-ray diffraction pattern diagram of brominated diketopyrrolopyrrole and C.I. pigment red 254.

[Fig. 5] The surface of the aromatic ring in the crystal of brominated diketopyrrolopyrrole and C.I. pigment red 254 is sawtooth (zig) A schematic representation of the sawtooth in a laminated structure of herringbone.

Fig. 6 is a schematic view showing the sawtooth in a laminated structure in which the faces of the aromatic rings in the crystals of the brominated diketopyrrolopyrrole and C.I. pigment red 254 are serrated in a zigzag pattern.

Fig. 7 is a schematic view showing the relationship between secondary particles, primary particles, crystallites, and crystal faces.

Form of implementing the invention

Preferred embodiments of the present invention are described below, but the present invention is not limited thereto.

The diketopyrrolopyrrole pigment fine particles of the present invention have any of the following (1) to (15).

(1) A diketopyrrolopyrrole pigment microparticle containing 90% or more of a compound represented by the following general formula (I), which is calculated by a X-ray diffraction pattern in a lattice plane (±1 ± Among the 8 faces of 1 ± 1), the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less. [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent].

(2) A diketopyrrolopyrrole pigment microparticle containing a compound represented by the following general formula (I), which is calculated by a X-ray diffraction pattern (±1 ± 1 ± 1) Among the eight faces, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less, and the (1 5 -1) plane direction is calculated by the X-ray diffraction pattern. The crystal size is below 80Å.

(3) A diketopyrrolopyrrole-based pigment microparticle containing a compound represented by the following general formula (I), which is an 8-sided surface of (±1 ± 1 ± 1) calculated by an X-ray diffraction pattern Among them, the crystallite size in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is divided by the lattice plane calculated by the X-ray diffraction pattern, and 2θ=3~10° The maximum peak corresponds to the crystallite size in the direction of the surface, and the ratio of the calculated crystallite size is 0.85 to 1.25, and the average primary particle diameter is 5 to 40 nm.

(4) A diketopyrrolopyrrole pigment fine particle containing 90% or more of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern and corresponds to 2θ = 24.5 ° ± 0.3 ° The crystallite size of the crystal lattice is less than 140 Å.

(5) A diketopyrrolopyrrole pigment fine particle containing 90% or more of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern and corresponds to 2θ = 24.5 ° ± 0.3 ° The crystallite size of the crystal lattice is below 140Å, calculated by X-ray diffraction pattern and 2θ=28.0°±0.3° The crystallite size of the corresponding lattice surface is 80 Å or less.

(6) The diketopyrrolopyrrole pigment fine particles according to the above item (1), (2), (4) or (5), wherein the average primary particle diameter is 5 to 40 nm.

(7) A diketopyrrolopyrrole pigment fine particle containing a compound represented by the following general formula (I), which is a crystal lattice corresponding to 2θ = 24.5 ° ± 0.3 ° calculated by an X-ray diffraction pattern The crystallite size of the surface is divided by the crystallite size of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern, and the ratio of the crystallite size calculated is 0.85 to 1.25, and the average The primary particle size is 5 to 40 nm.

(8) The diketopyrrolopyrrole pigment microparticles according to any one of the above items (1) to (7), wherein the maximum peak of 2θ=3 to 10° is calculated by the X-ray diffraction pattern The value of the surface spacing of the corresponding lattice surface at 80 ° C and the rate of change at 230 ° C (according to the following specific formula) are 3.0% or less, the value at 80 ° C and the value at 230 ° C. Rate of change = {(interval at 230 °C) / (interval at 80 °C) × 100} - 100 (%) [specific formula].

(9) The diketopyrrolopyrrole pigment microparticles according to any one of the above items (1) to (7), wherein the crystal corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern The value of the lattice surface spacing at 80 ° C and the rate of change at 230 ° C (according to the following specific formula) is 3.0% or less, the value at 80 ° C and the rate of change at 230 ° C ={(interval at 230 °C) / (interval at 80 °C) × 100}-100 (%) [Specific formula].

(10) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (9), wherein the standard deviation of the primary particle diameter is less than 7.0.

(11) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (10), wherein a coefficient of variation (CV value) of the primary particle diameter is less than 30.

(12) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (11), wherein the content of Fe is 35 ppm or less.

(13) The diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (12), wherein the general formula (I) is represented by the following general formula (II), [In the above general formula (II), R is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkyl group which may have a substituent, or An aryl group which may have a substituent].

(14) The ketopyrrolopyrrole pigment microparticles of the above item (13), wherein R is bromine represented by the following formula (III),

(15) A diketopyrrolopyrrole pigment microparticle containing a compound represented by the formula (III), which is 8 (±1 ± 1 ± 1) of a lattice plane calculated by an X-ray diffraction pattern Among the faces, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less.

(16) A pigment dispersion which is a pigment dispersion containing at least an organic pigment and an organic solvent, wherein the organic pigment is a diketopyrrolopyrrole pigment according to any one of the above items (1) to (15) Microparticles.

(17) A photosensitive coloring composition containing at least the diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (15).

(18) A color filter comprising at least the photosensitive coloring composition of the above item (17).

(19) A color filter comprising at least the diketopyrrolopyrrole pigment fine particles according to any one of the above items (1) to (15).

According to the present invention, it is possible to provide a photosensitive coloring composition using the diketopyrrolopyrrole pigment fine particles having any of the characteristics (1) to (15) described above, in particular, by using the pigment fine particles containing the same. Color filter made of the photosensitive coloring composition obtained from the pigment dispersion Since the light sheet is excellent in high contrast and high tinting strength and heat resistance, it is possible to provide a photosensitive coloring composition and a color filter having very suitable properties.

[Pigment species]

The pigment fine particle type pigment of the present invention is a fine particle containing a pigment of a diketopyrrolopyrrole pigment compound represented by the following general formula (I).

[In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. Or an aryl group which may have a substituent]

The diketopyrrolopyrrole pigment compound is, for example, obtained by various conventional production methods or various commercially available products.

For example, the basic method for producing a diketopyrrolopyrrole pigment compound, and the succinate synthesis method using a nitrile compound as a starting material, US Pat. No. 4,415,685, US Pat. No. 4,579,949, the disclosure of each of In the method, the type, number, and position of the functional group of the starting material are selected, and the type, number, and position of X ₁ and X ₂ of the above general formula (I) can be selected. In addition, various methods for improvement include, for example, JP-A-58-210084, JP-A-07-90189, JP-A-08-48908, WO2009/81930, EP1411092B1, and Japan Those who have obtained the method described in the publication No. 2012-211970 and the like.

The color index (C.I.) is described, for example, C.I.pigment red 254, C.I.pigment red 255, C.I.pigment red 264, C.I.pigment orange 71, C.I.pigment orange 73, etc., and various commercial products.

Among the diketopyrrolopyrrole pigment compounds represented by the general formula (I), in particular, the diketopyrrolopyrrole pigment represented by the following general formula (II) having a substituent at the (para) position The compound is excellent in color tone and is suitable for use as a red pigment.

[In the above general formula (II), R each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkyl group which may have a substituent, or Aryl group having a substituent]

Among them, C.I.pigment red 254 in which R is a chlorine atom, or brominated diketopyrrolopyrrole (the following formula (III)) in which R is a bromine atom has excellent light resistance, chemical resistance, high chroma, and brightness. It is also excellent in high optical properties, so it is suitable for color filter applications.

C.I.pigment red 254 differs from the brominated diketopyrrolopyrrole due to the different types of substituents. Compared with C.I.pigment red 254, the brominated diketopyrrolopyrrole shifts to a longer wavelength side and becomes a more bluish red color. With the color of the purpose, choose to use this.

In particular, the brominated diketopyrrolopyrrole represented by the above formula (III) is a sterive hindrance of a bromine atom, and the intermolecular bond is weaker than CIpigment red 254, so that it is easy to be micronized. It is better to use a color filter suitable for high contrast and high brightness, so it is better for color filter applications.

Further, in particular, the ratio of the crystallite size or the crystallite size of the present invention described below was calculated using brominated diketopyrrolopyrrole, and the inventors have found that the highest contrast can be obtained.

In addition to the diketopyrrolopyrrole pigment compound represented by the general formula (I), the pigment fine particles of the present invention may contain an organic pigment other than the diketopyrrolopyrrole pigment compound. In this way, particle size control or chromaticity adjustment can also be performed by containing other organic pigments. The organic pigment which can be used in combination at this time is not particularly limited, and examples thereof include a perylene pigment, a perinone pigment, a quinacridone pigment, a quinacridone anthraquinone pigment, and an anthraquinone pigment.蒽 蒽醌 颜料 pigment, benzimidazolone pigment, bisazo condensate pigment, disazo pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triaryl carbon (carbonium) Pigment, dioxazine-based pigment, amine-based lanthanide pigment, thioindigo pigment, isoporphyrin pigment, isoindolinone pigment, pyranthrone pigment, isopurine Isoviolanthrone is a pigment, or a composition and mixture thereof. The above organic pigments can also be used as their crude pigments.

[crystallite size] 1. First aspect of the present invention

In the first aspect of the present invention, the pigment fine particles of the present invention are characterized in that X-rays are among eight planes (±1 ± 1 ± 1) among the lattice planes calculated by the X-ray diffraction pattern. The crystallite size in the direction corresponding to the largest peak in the diffraction pattern (hereinafter referred to as "surface α") is 140 Å or less, and the compound represented by the above general formula (I) contains 90% or more.

The crystallite size in the direction of the surface α is 140 Å or less, preferably 130 Å or less, more preferably 120 Å or less, and most preferably 100 Å or less.

The content of the compound represented by the general formula (I) is 90% or more, more preferably 95% or more, still more preferably 97% or more, and most preferably 99% or more.

In the case where the pigment species is a compound represented by the above general formula (II), the surface α is a (1 1 1) plane as shown in Fig. 5, and corresponds to 2θ = 24.5 ° ± 0.3 °. Therefore, the pigment species is represented by the above general formula (II). In the case of the compound, the crystallite size corresponding to 2θ = 24.5 ° ± 0.3 ° is preferably 140 Å or less.

2. Second aspect of the present invention

In the second aspect of the present invention, the pigment fine particles of the present invention are characterized in that the crystallite size in the plane direction is 140 Å or less, and the (1 5 -1) plane calculated by the X-ray diffraction pattern (hereinafter referred to as "face" The crystallite size in the β") direction is 80 Å or less, and contains the compound represented by the above general formula (I).

The crystallite size in the direction of the surface α is 140 Å or less, preferably 130 Å or less, more preferably 120 Å or less, and most preferably 100 Å or less. The crystallite size in the β direction is preferably 80 Å or less, more preferably 75 Å or less, and still more preferably 70 Å or less. More preferably, the crystallite size in the α direction is 140 Å or less and the crystallite size in the β direction is 80 Å or less, and more preferably the crystallite size in the α direction is 130 Å or less and the crystallite size in the β direction is 75 Å or less. The crystallite size of the surface α direction is 120 Å or less and the crystallite size of the surface β direction is 70 Å or less. The crystallite size of the surface α direction is preferably 100 Å or less and the crystallite size of the surface β direction is 70 Å or less.

When the pigment species is a compound represented by the above general formula (II), the surface α is as described above (1 1 1), corresponding to 2θ=24.5°±0.3°, and the surface β is as shown in FIG. 6 (1 5 The -1) surface corresponds to 2θ=28.0°±0.3°. Therefore, in the case where the pigment species is a compound represented by the above general formula (II), the crystallite size corresponding to 2θ=24.5°±0.3° has a crystallite size of 140 Å or less, and corresponds to 2θ=28.0°±0.3°. The crystallite size of the crystal lattice is preferably 80 Å or less.

3. The third aspect of the present invention

According to a third aspect of the present invention, the pigment fine particles of the present invention are characterized by comprising the compound represented by the above general formula (I), which is obtained by dividing the crystallite size in the plane α direction by X-ray diffraction pattern Among the crystal lattice planes, the crystallite size in the direction corresponding to the largest peak of 2θ=3~10° (hereinafter referred to as “face γ”), the calculated crystallite size ratio is 0.85 to 1.25, and the average The primary particle size is 5 to 40 nm.

The ratio of the above crystallite size is preferably from 0.85 to 1.25, more preferably from 0.90 to 1.20, most preferably from 0.95 to 1.15. The average primary particle diameter is preferably 5 to 40 nm, more preferably 10 to 30 nm, most preferably 15 to 25 nm. In addition, the ratio of the crystallite size is 0.85 to 1.25 and the average primary particle diameter is 5 to 40 nm. Further, the ratio of the crystallite size is 0.90 to 1.20 and the average primary particle diameter is 10 to 30 nm. The ratio of the size is 0.95 to 1.15 and the average primary particle size is 15 to 25 nm.

When the pigment species is a compound represented by the above general formula (II), the surface α corresponds to the above (1 1 1) plane and corresponds to 2θ = 24.5 ° ± 0.3 °. The plane γ is the (0 2 0) plane shown in Figs. 5 and 6, and corresponds to 2θ = 7.4 ° ± 0.3 °. Therefore, in this case, the pigment fine particles of the present invention divide the crystallite size of the lattice plane corresponding to 2θ=24.5°±0.3° calculated by the X-ray diffraction pattern by the X-ray diffraction pattern. Calculating the crystallite size of the lattice plane corresponding to 2θ=7.4°±0.3°, the ratio of the calculated crystallite size is 0.85 to 1.25, and the average primary particle diameter is preferably 5 to 40 nm.

Especially in the case of the pigment species C.I.pigment red 254 When the ratio of the crystallite size is 0.85 to 1.25, more preferably 0.90 to 1.15, still more preferably 0.95 to 1.10. The average primary particle diameter is preferably 5 to 40 nm, more preferably 10 to 30 nm, most preferably 15 to 25 nm. In addition, the ratio of crystallite size is 0.85 to 1.25 and the average primary particle diameter is 5 to 40 nm, the ratio of crystallite size is 0.90 to 1.15, and the average primary particle diameter is 10 to 30 nm, and the ratio of crystallite size is better. It is preferably 0.95 to 1.10 and the average primary particle diameter is 15 to 25 nm.

Further, when the pigment species is brominated diketopyrrolopyrrole, the ratio of crystallite size is preferably 0.85 to 1.25, more preferably 0.90 to 1.20, and most preferably 0.95 to 1.15. The average primary particle diameter is preferably 5 to 40 nm, more preferably 10 to 30 nm, most preferably 15 to 25 nm. Further, the ratio of the crystallite size is 0.85 to 1.25 and the average primary particle diameter is preferably 5 to 40 nm, the ratio of the crystallite size is 0.90 to 1.20, and the average primary particle diameter is preferably 10 to 30 nm, and the ratio of the crystallite size is 0.95~1.15 and the average primary particle size is 15~25nm.

Table 1 shows the (02 0) plane, the (1 1 1) plane, the (1 5 -1) plane, and the Bragg angle (2θ) of the three lattice planes of the compound represented by the above general formula (II). relationship.

4. The fourth aspect of the present invention

In the fourth aspect of the present invention, the pigment fine particles of the present invention are characterized in that the crystallite size in the plane α direction is 140 Å or less and the compound represented by the above formula (III) (brominated diketopyrrolopyrrole) is contained.

Preferably, the ratio of the crystallite size in the α direction to the crystallite size in the preferred surface β direction, preferably the crystallite size ratio, and the primary particle size are the same as in the second and third aspects of the present invention. The content of the compound represented by the formula (III) is preferably the same as the content of the compound represented by the general formula (I) in the first embodiment of the present invention.

3. The effect of crystallite size and its ratio on performance 3-1 crystallite size

In general, it is known that the interface between the crystallites and the crystallites (crystal grain boundaries) constituting the primary particles is easily scattered by light, and the grain boundary is a cause of light scattering. Therefore, in order to increase the optical characteristics of the pigment fine particles, it is considered to reduce the area of the crystal grain boundaries in the fine particles, thereby reducing the influence of the crystal grain boundaries. Therefore, attempts have been made to reduce crystal grain boundaries in various fields. When the area of the crystal grain boundary is reduced, it is preferable that the crystallite size is larger. However, it has been unexpectedly reported by the present inventors that the pigment fine particles of the present invention having a smaller crystallite size have excellent optical characteristics as described above. The mechanism for exhibiting more excellent optical characteristics due to the crystallite size of the pigment fine particles of the present invention is not completely understood, but it is presumed as follows.

When the crystallite size is small, it constitutes the microcrystal between the primary particles. The number of interfaces (crystal grain boundaries) increases, but the area of each crystal grain boundary becomes small. Generally, when the area of the crystal grain boundary is large, light scattering is easy. On the other hand, in the present invention, it is presumed that by controlling the crystallite size to be small, the area of the crystal grain boundary becomes small, the light scattering is reduced, and the contrast and brightness of the obtained color filter are improved. Here, the crystallite size is such that the crystallite size in the α direction of the small finger plane is 140 Å or less, and the crystallite size in the β direction is 80 Å or less.

Further, as shown in Fig. 7, since the primary particles of the pigment are composed of crystallites, the primary particles can be made smaller by reducing the crystallite size. Because the primary particles are small, the color filter has a high transmittance, which reduces light scattering and improves contrast and brightness. Here, the small primary particle of the pigment means that the average primary particle diameter is 40 nm or less.

Further, when the diketopyrrolopyrrole pigment compound represented by the general formula (I) has an anisotropic crystal, it is impossible to completely prevent birefringence caused by the crystal itself due to the grain boundary. In particular, in the case of a diketopyrrolopyrrole pigment compound having a substituent at the (para) position (the above general formula (II)), it is a herringbone grain structure, and the space group is P21/n, which has a relative position in the para position. The substituent or the Tert-butyl-diketopyrrolopyrrole is a brick structure of a brick wall, and the space group is P1 (a bar (-) above P1), and the symmetry is low. And the anisotropy is high. Therefore, the crystallite size of the surface α is set to 140 Å or less, and the crystallite size of the surface β is set to 80 Å or less. As will be described later, it is possible to obtain more improved isotropic properties and excellent optical characteristics. As shown in the following number 1, a horizontal bar (-) is attached to P1.

Further, since the pigment fine particles of the present invention have small primary particles, it is possible to suppress an undesirable state such as generation of foreign matter due to coarse primary particles.

When the size of the crystallites is large, it is inevitable that the primary particles also become large. As the crystallite size increases, the primary particles also become larger, which hinders the contrast of the color filters and increases the brightness.

The crystallite size exceeds the upper limit of the range of the present invention. For example, when the crystallite size in the plane α direction exceeds 140 Å and the crystallite size in the plane β direction exceeds 80 Å, the resulting color filter has insufficient contrast and brightness. Moreover, it is easy to cause foreign matter to occur due to coarse particles.

Further, the lower limit of the crystallite size is not particularly limited, but if it is too small, the primary particles are also required to be smaller than necessary, and the specific surface area of the primary particles is increased. Since the specific surface area of the primary particles is increased, the surface energy of the particles is increased, and the dispersion of the pigment fine particles to the dispersion medium becomes difficult. Specifically, in the case of dispersion, the pigment fine particles are agglomerated, or the pigment dispersion in which the pigment fine particles are dispersed in the dispersion medium has a high viscosity, or the possibility of sticking or gelation with time changes becomes high. In order to stabilize the dispersion, since the pigment dispersion contains a large amount of a dispersant, the color filter obtained by the color filter has less colored components, and the color filter characteristics are increased due to unnecessary dispersant components, thereby causing color characteristics. There is a high probability of a step-down in the reduction or color filter fabrication. Further, the size of the crystallites is too small, which is technically difficult. On the contrary, it has been found by the present inventors that it is not necessary to be so small. Performance improvement. Therefore, it is sufficient to reduce the crystallite size to the above upper limit value.

3-2 crystallite size ratio and average primary particle size

By setting the ratio of the crystallite size of the face α to the face γ within the range of the present invention, for example, in the range of 0.85 to 1.25, a high contrast, high brightness color filter can be obtained. The mechanism in which the ratio of the crystallite size affects the optical characteristics of the color filter is not clear, but it is presumed as follows.

The ratio of the above crystallite size, that is, the aspect ratio (hereinafter also referred to as "the aspect ratio of the crystallite size") is small, meaning that the crystallite is close to a spherical shape. When it is close to a spherical shape, when primary particles are formed, the crystallites are closely packed, and in the primary particles, the crystallites are easily arranged in such a manner that the anisotropy is small. By reducing the anisotropy within the primary particles, the primary particles become optically uniform, thereby increasing contrast and brightness. Further, since the crystallites are close to a spherical shape, the primary particles formed by the aggregation of the crystallites also have a spherical shape and primary particles having a small aspect ratio. In the cured film containing the fine particles of the primary particles, the primary particles are close to a spherical shape, and the pigment fine particles become difficult to align, and the anisotropy of the cured film is reduced, thereby improving contrast and brightness.

Further, by setting the ratio of the crystallite size within the range of the present invention, the pigment dispersion in which the fine particles of the pigment are dispersed in the dispersion medium can also reduce the amount of the dispersant added, and can form a low viscosity and a good dispersibility. It is possible that the length and width of the primary particles are relatively small. Therefore, it is presumed that the specific surface area of the pigment fine particles formed by the primary particles is small, and pigment fine particles having a small surface energy of the particles can be obtained, thereby suppressing aggregation of the particles.

In the case where the aspect ratio of the above crystallite size exceeds the range of the present invention, the contrast and brightness of the obtained color filter are insufficient. In particular, in the present invention, each lattice plane (±1 ± 1 ± 1) plane (plane α) defining the ratio of the crystallite size to the crystallite size is calculated by the X-ray diffraction pattern and 2θ=3 It is a revolutionary discovery that the surface corresponding to the maximum peak of ~10° (surface γ) can be used as an indicator of the isotropic property and is reviewed by the present inventors.

However, even if the aspect ratio of the crystallites is small, if the average primary particle diameter is large, the contrast and brightness of the resulting color filter are lowered. In addition, when the average primary particle diameter is 5 nm or less, even if the ratio of the crystallite size is within the above range, the specific surface area of the primary particles becomes large, and aggregation tends to occur, so that it is difficult to obtain a good dispersion. Therefore, the ratio of the size of the crystallite alone is within the above range, and the primary particle diameter is also within the above range. For example, in the case of the pigment fine particles having an average primary particle diameter of 5 to 40 nm, high contrast and high brightness can be obtained. Color filter.

[Measurement of crystallite size]

As described above, the crystallite size can be measured by correlating the Bragg angle (2θ) of the X-ray diffraction spectrum with the lattice plane of the crystal structure.

In the diketopyrrolopyrrole pigment, the crystal structure of CIpigment red 254 is analyzed in the literature (Acta. Cryst. B49, 1056 (1993)) by X-ray crystal structure analysis, and the pigment species is CIpigment red 254. Use this to measure the crystallite size. Brominated diketopyrrole The X-ray diffraction pattern of pyrrole is shown in Figure 4. Compared to CIpigment red 254, the X-ray diffraction intensity is different, but the peak position appears in the same place, so the brominated diketopyrrolopyrrole can be It is assumed that the crystal lattice structure similar to CIpigment red 254 and the crystal lattice surface of the crystal structure are analyzed. In the case of other diketopyrrolopyrrole pigments, the crystal structure is analyzed by the X-ray diffraction pattern so that the Bragg angle (2θ) of the X-ray diffraction spectrum corresponds to the lattice plane of the crystal structure.

In the present invention, the measurement of the crystallite size of each of the lattice faces described above is based on the following conditions and order.

(1) The sample was measured by powder X-ray diffraction using a CuKα line, and the Bragg angle (2θ) was in the range of 5.3° to 60°.

(2) From the X-ray diffraction pattern obtained in (1), the diffraction pattern after removing the background is obtained. In the method of removing the background, the Bragg angle (2θ)=5.3° and the vicinity of 6.5°, the vicinity of 10°, and the lower end of 60° of the above-mentioned measurement pattern are respectively connected by a straight line as a background, and the X-ray obtained by (1) is obtained. The value of the intensity of the shot removes the operation of the pattern of the X-ray diffraction intensity values represented by this background.

(3) The X-ray diffraction pattern obtained by (2), the Bragg angle (2θ) of the diffraction peak characteristic of the (0 2 0) plane, respectively, in the compound of the general formula (II) The Bragg angle (2θ) of the diffraction peak characteristic of the diffraction peak near the vicinity of 7.4°±0.3° and the (1 1 1) plane = the diffraction peak near 24.5°±0.3°, (1 5 -1) plane The Bragg angle (2θ) of the characteristic diffraction peak = a diffraction peak near 28.0 ° ± 0.3 °, and the half width and the Bragg angle (2θ) of the diffraction peak are obtained. The calculation of the full width at half maximum uses commercially available data for each of the three diffraction peaks present in the above measurement range. Analyze the software and perform peak separation to calculate. For example, in the embodiment described later, the data analysis software HighScorePlus Ver. 3.0e (3.0.5) manufactured by PANalytical Co., Ltd. is used, and the peak shape is used as a Pseudo Voigt function, and the value of the full width at half maximum is calculated using Fitting.

(4) The crystallite size is calculated by the half-height width of the diffraction peak calculated in (3) and the formula of Scherrer described below.

D=K λ /(B×cosA)

B=Bobs-b

Here, D: crystallite size (Å)

Bobs: full width at half maximum (rad) calculated by (3)

b: X-ray diffraction device angular resolution correction factor, half-height width (rad) of standard 矽 crystal measurement. The standard crystallization was measured by the following device configuration and measurement conditions, b = 0.087.

A: diffraction peak Bragg angle 2θ (rad)

K: Scherrer constant (defined as K=0.90)

λ: X-ray wavelength (Å) (for CuKα line, λ=1.54)

The measurement conditions are as follows in detail.

X-ray diffraction device: multi-purpose X-ray diffraction device X'Pert P manufactured by PANalytical

Owder protractor (goniometer): high precision sample horizontal protractor made by PANalytical

Sampling width: 0.0131°

Step time: 0.335 seconds

Divergence slit: program divergence slit

Incident side scattering slit: none

Incident side parallel plate slits (soller slits): 0.04°

Incident side mask: 10mm

Light-receiving side scattering slit: 8mm

Light-receiving side parallel plate slit: 0.04°

Tube ball: Cu

Tube voltage: 45kV

Tube current: 40mA

Further, as long as it is a method in which the same results as the above methods are obtained, other methods may be employed.

[Calculation of the ratio of crystallite size]

The crystallite size of each surface obtained by the above method is calculated by dividing the crystallite size of the (1 1 1) plane by the crystallite size of the (0 2 0) plane, and calculating (1 1 1) plane and (0) 2 0) The ratio of the crystallite size of the face.

[The rate of change in the surface spacing of the lattice plane]

The diketopyrrolopyrrole pigment microparticles of the present invention are obtained by the X-ray diffraction pattern before and after heating, and the surface spacing of the lattice plane corresponding to the maximum peak of 2θ=3~10° is at 80 ° C and The rate of change of the value at 230 ° C (by the following specific formula) is preferably 3.0% or less. More preferably, it is 2.0% or less, and particularly preferably 1.5% or less.

The rate of change at 80 ° C and the value at 230 ° C = {(230 ° C Face spacing) / (face spacing at 80 ° C) × 100} - 100 (%) [Specific formula]

Here, C.I.pigment red 254 and brominated diketopyrrolopyrrole 2θ=7.4°±0.3° become the largest peak in 2θ=3~10°, corresponding to the (0 2 0) plane. (0 2 0) The surface of the surface is substantially perpendicular to the long axis of the crystal lattice. Compared with other lattice surfaces, the rate of change of the surface spacing due to heating is the largest, so it can be an indicator of the stability of the crystal structure described later. .

The other diketopyrrolopyrrole pigment is also the same as CIpigment red 254 or brominated diketopyrrolopyrrole, and the surface corresponding to the largest peak of 2θ=3~10° becomes a plane substantially perpendicular to the long axis of the crystal lattice. Compared with other lattice surfaces, the rate of change of the surface spacing due to heating is the largest, so it can be an indicator of the stability of the crystal structure.

When the color filter is manufactured, the step of heating the pigment is caused, and the color characteristics are deteriorated due to the heating. Specifically, there is a problem in that the hue shifts, the contrast, and the brightness decrease due to heating. On the other hand, in the pigment fine particles of the present invention, the rate of change of the surface interval is set to 3.0% or less, whereby deterioration of color characteristics due to heating can be suppressed, and a color filter having higher quality can be obtained.

In the present invention, by using pigment fine particles having a small change in the surface spacing of the lattice surface, a mechanism for obtaining a color filter having more excellent optical characteristics can be obtained, and a fine particle size or a crystallite size of a small crystallite size can be obtained. A mechanism in which the pigment fine particles having a small length and a width are small, and the rate of change in the surface interval of the lattice surface can be lowered, although it is not clear, it is presumed as follows.

In most cases, the direction of the expansion of the plane varies in the direction in which the lattice spacing changes due to heating. When the surface spacing is extended, the microcrystalline The area of the crystal grain boundary becomes large, and as described above, it becomes a primary particle which is easy to scatter light, and it is presumed that the pigment fine particles are liable to cause contrast or decrease in brightness. Further, it is presumed that the large change rate of the surface interval due to heating indicates that the crystal structure is unstable, the crystal structure changes due to heating, and the hue shift occurs due to the interaction of the electron orbitals of adjacent molecules.

It is considered that the reason why the rate of change in the surface interval due to heating becomes large is that the crystal structure contains many unstable elements. Examples of the unstable element of the crystal structure include strains such as impurities, amorphous components, and crystal structures. When the crystallite size is various, or when the length and width of the crystallite are relatively large, the crystal structure has strain, or the adjacent portion of the crystallite contains many unstable amorphous structures, and it is presumed that the crystal structure changes due to heating. The interaction of the electron orbitals of adjacent molecules produces a shift in hue. Further, it is considered that the amorphous structure which is unstable is heated and crystallized to generate foreign matter. On the other hand, since the fine particles of the pigment of the present invention are small in size and close to a spherical shape, it is presumed that the strain of the crystal structure is small, compact and stable, and the change in the crystal structure due to heating is suppressed, and the rate of change in the surface interval is small.

When the pigment fine particles of the present invention having a specific crystallite size or a specific crystallite size ratio are used, the crystal grain boundary which is a cause of the unstable structure of the crystal structure can be lowered, and the crystallites are tightly packed. Crystal structure. Therefore, the rate of change in the surface interval due to heating can be controlled within the above range, for example, within 3.0%. That is, a pigment having a small change in the surface interval due to heating and a stable crystal structure.

Further, the method of measuring the rate of change in the surface interval of the lattice surface by heating is carried out as follows.

(1) Similarly to the above [Measurement of crystallite size], powder X-ray diffraction measurement was performed by heating using a CuKα line in a range of 5.3° to 50° in Bragg angle (2θ). Specifically, first, the X-ray diffraction pattern was measured at 25 ° C, and then the temperature was raised to 80 ° C. After the temperature was maintained for 10 minutes, the X-ray diffraction pattern at 80 ° C was measured. Further, the temperature was raised to 230 ° C, and after the temperature was maintained for 10 minutes, the X-ray diffraction pattern at 230 ° C was measured.

(2) From the X-ray diffraction pattern obtained in (1), the diffraction pattern after removing the background is obtained. The background removal method is such that the Bragg angle (2θ) of the above measurement pattern is near 5.3°, and the vicinity of 6.5°, the vicinity of 10°, and the lower end of 37.5° are respectively connected by a straight line as a background, and the X-ray obtained by (1) is obtained. The value of the intensity of the shot removes the pattern of the value of the X-ray diffraction intensity represented by this background.

(3) The X-ray diffraction pattern obtained by the removal of the background obtained by (2), using the data analysis software HighScorePlus Ver. 3.0e (3.0.5) manufactured by PANalytical Co., Ltd., and fitting the peak shape as a Pseudo Voigt function (Fitting) The Bragg angle (2θ) of the diffraction peak characteristic of the (0 2 0) plane is calculated by the formula of Bragg angle = the surface interval of the diffraction peak in the vicinity of 7.4 ° ± 0.3 °.

2dsinA=nλ

Here, d: face spacing (Å)

A: diffraction peak Bragg angle 2θ (rad)

λ: X-ray wavelength (Å) (due to CuKα line, λ=1.54)

n: integer

(4) The rate of change of the surface interval due to these temperature changes was calculated by the following specific formula as a result of the interfacial spacing of the (0 2 0) plane at 80 ° C and 230 ° C obtained in (3).

The rate of change at 80 ° C and the value at 230 ° C = {(area spacing at 230 ° C) / (area spacing at 80 ° C) × 100} - 100 (%) [Specific formula]

The details of the measurement conditions are the same as those of the above [Measurement of crystallite size].

Further, as long as it is a method in which the same results as the above methods are obtained, other methods may be employed.

[primary particle size]

In the third aspect of the present invention, the diketopyrrolopyrrole pigment fine particles have a primary particle diameter of 5 to 40 nm. Further, in the diketopyrrolopyrrole pigment fine particles of the first, second, and fourth embodiments of the present invention, the primary particle diameter is preferably 5 to 40 nm. In any case, the primary particle diameter is preferably from 10 to 30 nm, particularly preferably from 15 to 25 nm. Further, the standard deviation of the primary particle diameter is preferably less than 7.0, more preferably less than 6.0, and particularly less than 4.0. Further, the coefficient of variation of the primary particle diameter (CV value: "CV value" below) is preferably less than 30, more preferably less than 28, and particularly less than 25.

By setting the primary particle diameter of the diketopyrrolopyrrole pigment fine particles to the above upper limit value, a highly contrast pigment dispersion can be obtained. In addition, by setting the primary particle diameter of the diketopyrrolopyrrole pigment fine particles to the above lower limit value, the viscosity at the time of preparing the dispersion can be lowered. It also inhibits the change in viscosity over time.

In the case of the diketopyrrolopyrrole pigment fine particles having a primary particle diameter exceeding the above upper limit value, the contrast may be lowered, and the performance required for use as a color filter may not be satisfied. In the case of a diketopyrrolopyrrole pigment fine particle having a primary particle diameter which does not reach the above lower limit value, the pigment fine particles are difficult to disperse in the dispersion medium, and the dispersion or the binder of the pigment dispersion is dispersed during the treatment. Since the amount of the compound such as a resin or a pigment derivative is extremely large, it is difficult to apply the pigment dispersion to a color filter.

By setting the standard deviation of the primary particle diameter of the diketopyrrolopyrrole pigment fine particles to the above upper limit value, a pigment dispersion having a high contrast and a low viscosity and a small change in viscosity with time can be obtained. When the standard deviation of the primary particle diameter exceeds the above upper limit value, many primary particles having different sizes or shapes are present, and the contrast of the pigment dispersion is likely to be lowered.

By setting the CV value of the primary particle diameter of the diketopyrrolopyrrole pigment fine particles to the above upper limit or less, a pigment dispersion having a high contrast and a low viscosity and a small change in viscosity with time can be obtained. When the CV value of the primary particle diameter exceeds the above upper limit value, many primary particles having different sizes or shapes are present, and the contrast of the pigment dispersion is likely to be lowered.

Here, the primary particle diameter is a particle diameter calculated from an image observed by an electron microscope. The measurement method of the primary particle diameter and its standard deviation and CV value is as follows.

10 parts by weight of the pigment fine particles of the present invention as a dispersing agent "BYKLPN 6919" (manufactured by BYK-Chemie Co., Ltd.) is 5 parts by weight of solid content, 1 part by weight of a sulfonated derivative of CIpigment red 254 as a dispersing aid, and propylene glycol monomethyl ether as an organic solvent of a dispersing medium. 70 parts by weight of the acetate was mixed and stirred for 6 hours using a paint mixer (manufactured by Asada Iron Works Co., Ltd.) to obtain a pigment dispersion. The pigment dispersion was diluted 50-fold to 200-fold with propylene glycol monomethyl ether acetate, and the dilution was treated by a ultrasonic homogenizer (manufactured by SND Corporation, ultrasonic cleaning machine US-105) for 5 minutes. After that, observe the particle image. This observation was observed using an S-5200-shaped electric field release scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) at an observation magnification of 20 kV at an acceleration voltage of 100 kV, and 100 particles which were clearly recognized by the observation image were used. SEM was used to measure the long diameter of the image analysis software (Scandium manufactured by OLYMPUS), and the primary particle diameter, the standard deviation, and the CV value were calculated.

[Content of diketopyrrolopyrrole compound]

The pigment fine particles according to the first aspect of the present invention contain 90% or more of the compound represented by the general formula (I). Thus, by containing the compound represented by the general formula (I) at a high concentration, the coloring power or brightness can be highly maintained. In order to reduce the crystal of the pigment fine particles, for example, a component that suppresses the growth of the particles (for example, a pigment derivative described in Patent Document 5) may be added. However, when such a component is added, it becomes difficult to maintain the coloring power or the brightness at a high level. In addition, the pigment fine particles of the first aspect of the present invention contain the compound itself represented by the general formula (I) in addition to the components such as the pigment derivative. The amount, which maintains a high content of 90% or more, can maintain the coloring power or brightness at a high level.

Further, in the case of the pigment fine particles of the second embodiment and the third aspect of the present invention, in order to maintain the coloring power or the brightness at a high level, the content of the compound represented by the formula (I) is preferably 90% or more, and is preferable. In the pigment fine particles of the fourth aspect of the present invention, the content of the brominated diketopyrrolopyrrole represented by the formula (III) may be 90% or more, and is preferably.

The content of the diketopyrrolopyrrole pigment compound represented by the general formula (I), the general formula (II), and the formula (III) can be determined as follows. The solvent extract of the pigment microparticles of the present invention is subjected to LC-MS analysis or NMR analysis to identify the components and quantitative analysis. More specifically, the pigment fine particles are dissolved in an organic solvent such as tetrahydrofuran (hereinafter referred to as "THF"), and subjected to molecular weight analysis by LC-MS liquid chromatography. Further, the insoluble matter was directly introduced into the probe as a solid, and molecular weight analysis was performed. These methods are based on the molecular information of the whole and part of the molecule and identify the ingredients. Further, the diketopyrrolopyrrole pigment compound represented by the general formula (I), the general formula (II), and the formula (III) of the pigment microparticles can be quantitatively analyzed in comparison with the standard component of the identification component. Further, the pigment fine particles were dissolved in heavy dimethyl hydrazine or heavy sulfuric acid, and each component was identified by NMR measurement, and the amount was determined by the area ratio of the NMR spectrum.

[Performance of Pigment Microparticles of the Present Invention]

The pigment fine particles of the present invention described above have excellent optical characteristics. Specifically, the contrast when used as a cured film of chromaticity x = 0.6500 is More than 7,000, more preferably 8,000 or more, but also 10,000 or more. Further, the film thickness for chromaticity x = 0.6500 may be 2.80 μm or less, particularly 2.70 μm or less, or 2.60 μm or less. Further, in the chromaticity x = 0.6500 and y = 0.3230, the luminance is 18.00 or more, and further, it is 19.00 or more, and a color filter excellent in optical characteristics can be obtained. The production of the cured film will be described later.

Here, one of the indexes of the color characteristics of the contrast pigment is preferable because the color is rich in color when used for an optical material such as a display. The contrast measurement is performed by using a contrast measuring device for the amount of light transmitted by the cured film sandwiched between the two polarizing plates and the light transmitted by the polarizing plate on the front side and the polarizing surface on the rear side in parallel and at right angles. CT-1) manufactured by Husui Electric Co., Ltd. measures the brightness of the polarizing plate as the brightness of the polarizing plate, and the ratio of the brightness of the polarizing plate when the polarizing surface is parallel and the brightness at the right angle to contrast ((contrast) = (polarized surface of the polarizing plate) It is calculated as the brightness in parallel) / (the brightness when the polarizing surface of the polarizing plate is a right angle).

Further, when the film thickness of the cured film is the same chromaticity and is thin, the photosensitive coloring composition can be saved, and when the film thickness is adjusted to the same film thickness, a cured film having a high coloring power can be obtained, which is preferable. The film thickness uses a non-contact surface. The layer cross-sectional shape measurement system (R5300G-Lite, manufactured by Ryo Chemical Co., Ltd.) was measured.

The heat resistance is expressed by the rate of change of the comparison {(comparation after the post-baking step - comparison after the post-baking step) / after the post-baking step × 100 (%)}.

Further, when the cured film was observed at 500 times using an optical microscope, the number of coarse particles was confirmed to be 50 or less, and further 20 or less.

Further, the brightness is one of the indexes of the color characteristics of the same pigment, and the value of the contrast and the brightness is higher. When used in an optical material such as a display, the color is rich in color and the amount of light in the backlight can be suppressed, which is preferable. The measurement of the brightness was carried out by using a spectrophotometer (LCF-1100, manufactured by Otsuka Electronics Co., Ltd.) for the cured film.

By the pigment fine particles of the present invention having a specific crystallite size or a specific crystallite size ratio, a mechanism for providing a color filter having extremely excellent optical characteristics as described above is not clear, but as described above, it is presumed that The size of the crystallites, for example, the crystallite size in the direction of the surface α, is controlled to be below 140 Å, the crystallite size in the β direction is controlled below 80 Å, or the ratio of the crystallite size is controlled, for example, in the range of 0.85 to 1.25. It can suppress the occurrence of crystal strain and the like, contribute to structural stability, and has little change when heated (by reducing the change due to heating to improve performance). Further, it is presumed to contribute to suppressing light scattering or the like (the influence of the optical properties of the crystal grain boundaries) which affects the crystal interface. In addition, it is estimated that the ratio of the size of the crystallites to the size of the crystallites is such that the size and shape of the primary particles are reduced, and the isotropic properties are formed, which contributes to the presence of the primary particles in a favorable state in the cured film (once). The effect of the state of the particles in the cured film). It is presumed that the multiplying effect of the plurality of elements achieves the excellent effect of the present invention, and it is difficult to achieve it by the prior art.

Further, in the cured film such as a color filter or in the photosensitive coloring composition, the general formula (I), the general formula (II), and the formula (III) represent The content of the diketopyrrolopyrrole pigment compound can be determined as follows. The solvent extract of the cured film or the photosensitive coloring composition is subjected to LC-MS analysis or NMR analysis to identify the components and quantitative analysis. More specifically, the cured film or the photosensitive colored composition is dissolved in an organic solvent such as THF, and subjected to molecular weight analysis by LC-MS liquid chromatography. Further, the insoluble matter was directly introduced into the probe as a solid, and molecular weight analysis was performed. Further, the diketopyrrolopyrrole pigment compound represented by the general formula (I), the general formula (II), and the formula (III) of the cured film or the photosensitive coloring composition can be compared with the standard substance of the identified component. Perform quantitative analysis. Further, the cured film or the photosensitive colored composition was dissolved in heavy dimethyl hydrazine or heavy sulfuric acid, and each component was identified by NMR measurement, and the ratio was determined by the area ratio of the NMR spectrum.

[Production method]

The method for producing the diketopyrrolopyrrole pigment microparticles of the present invention is not particularly limited, and a so-called salt polishing method, a so-called reprecipitation method, or a method of refining an organic pigment in which a salt polishing method and a reprecipitation method are combined may be used. It is manufactured by the various conventional techniques mentioned above.

Among them, it is preferable to use the control of the crystallite size or the primary particle diameter, and it is preferable to use a reprecipitation method in which the salt polishing method generates a pigment crystal strain due to excessive energy. In the reprecipitation method, a solution in which an organic pigment is dissolved in a good solvent (hereinafter also referred to as "pigment dissolving solution") and a weak solvent (hereinafter also referred to as "weak solvent") in which an organic pigment is dissolved in the good solvent are continuously continuous. Supplying a reaction field, mixing the two to cause precipitated pigment particles It is preferable to take out from the liquid and continuously carry out the pigment precipitation reaction by a continuous reaction apparatus.

In particular, the mixture of pigment solution and weak solvent can be used close. It is most suitable to carry out the mixing by a reaction apparatus (hereinafter also referred to as "fluid processing apparatus") which is capable of separating the surfaces which can be rotated relative to each other. The reaction device is formed in close proximity. In the special environment where the separation state is relatively rotated between the processing surfaces and the film fluid forced by the processing surface, the pigment solution and the weak solvent are mixed and the pigment particles are precipitated, and the conventional microreactor or the like Mixing device with obvious separation. Also, the pigment solution and the weak solvent are close to each other. The state of separation is mixed with a small interval between the processing surfaces for the rotation, and the influence of gravity is substantially eliminated. Further, the precipitation of the pigment particles using the reaction device is preferably under laminar flow conditions, rather than turbulent flow conditions. .

The preferred reasons for this method are as follows.

First, in the case of a method of mechanically pulverizing a pigment by a salt polishing method, the crystallite size is pulverized to, for example, a crystallite size of 140 Å or less in the plane α direction and a crystallite size of 80 Å or less in the plane of the surface β. Very big force. Further, since the crystallization is accompanied by crystal growth, it is necessary to prepare a state in which the reaction is balanced, and it is difficult to control and productivity is also poor. In the case of the reprecipitation method, once the pigment is dissolved, the control of the particle size is easier. However, in the case of the reprecipitation method, it is not easy to control to the crystallite size. When the reaction continues, the crystallites gradually grow, so this phenomenon must be prevented. Therefore, it is considered that the contact of the pigment solution in the reaction field with the weak solvent proceeds rapidly, and it is important to generate a large amount of particles having a small crystallite size. Therefore, the diffusion coefficient of the reaction field becomes It is important. Therefore, it is considered that a continuous reaction apparatus for continuously recovering the generated pigment fine particles by continuously supplying the pigment solution and the weak solvent to the reaction field is preferred. In particular, the mixture of pigment solution and weak solvent can be used close to. In the case of a reaction apparatus in which the separation process is performed continuously between the surfaces for the relative rotation, the diffusion coefficient of the reaction field is increased, and a large number of crystal nuclei are formed, whereby fine crystallite fine particles can be efficiently obtained.

Reprecipitation, especially in close proximity. The method of continuously performing the precipitation reaction of the pigment fine particles between the processing surfaces for the relative rotation of the separation, the obtained pigment fine particles are very fine, and one particle is uniformly produced, and the crystallite size and distribution thereof are small. In other words, the obtained pigment fine particles are fine fine particles having a small number of coarse particles and having a uniform particle diameter, and suppress the occurrence of crystal strain or the like. It is presumed that this is because the contact between the pigment solution and the weak solvent is carried out at a very high speed as described above, so that the diffusion coefficient of the reaction field becomes large, and a large amount of fine crystallites can be obtained, and fine pigment crystal aggregates can be obtained. The microparticles and the excess energy supplied by the pulverization treatment such as the salt grinding treatment are not applied, and the generation of strain can be suppressed.

In the state in which the fine particles of the pigment obtained by the above method are in the form of crystals or the like, and the coarse particles having the coloring property are inhibited, a pigment fine particle dispersion excellent in heat resistance and coloring property can be obtained. In other words, not only the primary particle diameter of the pigment fine particles but also the size or distribution of the crystallites can be controlled, and a color filter which improves the characteristics of color characteristics and heat resistance and maintains excellent performance can be obtained.

The production of the pigment fine particles of the present invention by the reprecipitation method can be specifically carried out as follows. First, the diketopyrrolopyrrole The pigment precursor (hereinafter also referred to as "pigment") is dissolved in a good solvent. The pigment original system refers to the pigment before the micronization treatment described below. The diketopyrrolopyrrole-based pigment precursor is not particularly limited, and a commercially available pigment can be used, and a pigment produced by various methods disclosed in the prior art for the method for producing a diketopyrrolopyrrole pigment can be used.

The good solvent for dissolving the diketopyrrolopyrrole pigment precursor may, for example, be water or an organic solvent or a mixed solvent of a plurality of them. Examples of the water include tap water, ion-exchanged water, pure water, ultrapure water, and RO water. Examples of the organic solvent include an alcohol solvent, a guanamine solvent, a ketone solvent, an ether solvent, an aromatic solvent, carbon disulfide, and fat. A family solvent, a nitrile solvent, an anthraquinone solvent, a halogen solvent, an ester solvent, an ionic liquid, a carboxylic acid compound, a sulfonic acid compound, or the like. The above solvents may be used singly or in combination of plural or more.

Here, an inorganic hydroxide such as sodium hydroxide or potassium hydroxide, or a compound such as a metal alkoxide such as sodium methoxide or potassium tert-butoxide or a quaternary ammonium compound may be present in the above-mentioned good solvent. People know. In the present invention, it is particularly preferred to add a quaternary ammonium compound to the above good solvent. It is particularly easy to control the characteristics of the present invention to a specific crystallite size and primary particle diameter by adding a quaternary ammonium compound to the above-mentioned good solvent. Although the mechanism is not clear, the presence of the quaternary ammonium compound in the solvent brings good results to the dissolution of the diketopyrrolopyrrole compound pigment precursor and subsequent precipitation, especially for improving the color characteristics. result.

Quaternary ammonium compound can be added, benzyl trimethyl can be used a hydroxide, a chloride or a bromide of ammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium or tetrahexylammonium, but it is preferably from the viewpoint of improving solubility. The hydroxide is particularly preferably benzyltrimethylammonium hydroxide or tetramethylammonium hydroxide. These can be used alone or in combination of two or more types.

In addition to these, tetradecyldimethylbenzylammonium chloride or tetra-N-butylammonium tribromide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate or the like can also be used.

The amount of the quaternary ammonium compound added is preferably 0.1 to 10 mol equivalents with respect to the pigment precursor, and more preferably 0.3 to 6 mol equivalents, more preferably 0.5 to the pigment original. 4 molar equivalents. By adding 0.1 mol equivalent or more to the pigment original, the dissolution of the pigment precursor can be sufficiently performed, which is advantageous in the precipitation step of the pigment fine particles, and the occurrence of coarse particles can be suppressed. In addition, by suppressing the amount of the pigment precursor of the solvent to 10 mol equivalent or less with respect to the pigment original, it is preferable to obtain a good productivity, and it is preferable to suppress the decomposition of the molecules of the pigment precursor. It is preferable because it can provide a better influence on heat resistance and color characteristics.

The preparation method of the pigment solution is not particularly limited, but it is preferably prepared by using a stirrer having a rotating stirring blade. Therefore, it is of course possible to suppress the occurrence of coarse particles in the undissolved matter in the pigment solution and to dissolve two or more molecules or elements, and to rapidly produce a more uniform dissolved state of the pigment.

Presumably by using a mixer with rotating stirring blades By preparing a pigment solution, a pigment solution which forms a uniform dissolved state or a molecularly dispersed state at a molecular level can be obtained, and the dissolved state of the pigment solution or the state of forming a cluster can be improved.

The mixer for preparing the pigment solution is not particularly limited as long as it has a stirring blade for rotating the stirring blade. Generally, a mixer having a rotating stirring blade has a peripheral speed of 1 m/sec or more at the front end of the stirring blade. . It may be carried out at a low peripheral speed of less than 1 m/sec, but from the viewpoint of shortening the time during which the pigment is dissolved or improving the reliability of the pigment dissolution, a stirrer which rotates at a high speed is preferable. The pigment solution is prepared at a peripheral speed of 1 m/s or more, preferably 10 m/s or more, from the viewpoint of suppressing the occurrence of coarse particles. Such a stirrer is preferably various dispersing machines such as a high-speed rotary emulsification disperser (manufactured by M-technique Co., Ltd., product name: CLEARMIX).

The concentration of the diketopyrrolopyrrole pigment original in the pigment solution is preferably higher in terms of a productive surface. It is preferably contained in an amount of 3% by weight or more, more preferably 5% by weight or more.

The pigment solution is mixed with the above weak solvent to precipitate fine particles of the pigment. As the solvent to be used for the weak solvent, a solvent exemplified as a good solvent for dissolving the diketopyrrolopyrrole pigment precursor can be used, but it is necessary to select a solvent having a low solubility for the organic pigment contained in the pigment solution. These solvents may each be used singly or in combination of plural or more. Further, in order to adjust the pH, adjust the particle diameter, and the degree of crystallization, an acid may be added. When the acid to be added is an organic acid, a carboxylic acid such as formic acid, acetic acid, propionic acid or citric acid, benzenesulfonic acid, cyclohexanesulfonic acid or p-toluenesulfonic acid can be used. Phenolic acids such as sulfonic acid, salicylic acid, cresol, thymol, and the like. Further, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, hexafluorophosphoric acid, aminosulfonic acid or perchloric acid may also be used. These may each be used singly or in combination of plural or more. By adding an acid, it is sometimes possible to bring about a further improvement in color characteristics. Further, in the step of preparing the weak solvent, it is preferable to use the agitator having the rotating stirring blade as in the preparation of the pigment solution.

The above pigment solution and a weak solvent are mixed to precipitate fine particles of the pigment. As mentioned above, the mixture of the two can be close. It is preferred to continuously mix the surfaces for the relative rotation of the separation.

The temperature at which the pigment particles are precipitated is important for the adjustment of the primary particle size and the control of the crystallite size. Specifically, by adjusting the temperature of both the pigment solution and the weak solvent, the temperature at the time of precipitation becomes 50° C. or lower, and finer particles can be precipitated. Particularly preferably, the temperature at the time of precipitation is 30 ° C or less. When the precipitation of the pigment fine particles is carried out at a high temperature of more than 50 ° C, the crystal growth of the pigment fine particles is promoted, and coarse particles are precipitated, and when the pigment fine particles are precipitated at 50 ° C or lower, the crystal growth of the fine particles is suppressed, and the crystallite size is suppressed. Smaller, fine-grained and uniform pigment particles will precipitate.

By mixing the pigment solution and the weak solvent, the pigment fine particles are precipitated, and the obtained slurry containing the pigment fine particles is subjected to filtration, centrifugation, dialysis, critical filtration, or the like, and the pigment fine particles are taken out from the liquid to use various solvents. Washed, the pigment microparticles of the present invention can be isolated. The solvent used for washing can be optionally used as a solvent for dissolving the aforementioned diketopyrrole A solvent exemplified as a good solvent for a pyrrole-based pigment precursor. Further, in the case of the washing treatment, it is preferred to use the above-described agitator having a rotating stirring blade. The end point of the washing is not particularly limited, and can be determined by analysis of the pH of the washing liquid, ions of impurities, or organic matter. Moreover, since the pigment fine particles after washing have a state of washing the solvent used at the end of the washing, it is necessary to perform drying or solvent replacement.

The drying method is not particularly limited, and examples thereof include vacuum drying, warm air drying, freeze drying, and the like. The powder of the pigment fine particles can be obtained by drying.

The method of solvent substitution is not particularly limited. After the washing is completed, the obtained wet cake containing the fine particles of the cleaning liquid is placed in a solvent of interest, and the liquid is uniformly stirred, and then filtered and centrifuged again. By means of separation, dialysis, critical filtration, etc., a wet cake of the desired pigment microparticles containing the solvent can be produced.

The precipitation of the fine particles of the reprecipitation method and the washing treatment of the precipitated fine particles of the pigments can be said to be a process of not only precipitating the fine particles of the pigment but also purifying the pigment precursor. It is presumed that impurities such as a metal or an unreacted substance incorporated in the fine particles of the pigment are extracted by dissolving the pigment precursor in a state of the molecule, and the fine particles are precipitated and washed to remove the impurities. The inventors of the present invention consider that one of the reasons for the excellent coloring power of the pigment fine particles by the reprecipitation method is the purification of the above-mentioned pigment precursor compared to the salt milling method represented by Patent Documents 1 and 2. .

When the amount of Fe contained in the pigment fine particles is large, the pigment is used. When a color filter is produced by a microparticle, the liquid crystal may be malfunctioning due to a decrease in the voltage holding ratio. In addition, since the amount of Fe contained in the pigment fine particles is large, not only the amount of impurities contained in the color filter is increased, but also the color characteristics or the coloring power are lowered, and the color filter may be formed in the subsequent baking step. The cause of foreign matter on the coating film. Therefore, it is necessary to minimize the amount of Fe contained in the pigment fine particles. It was found that the amount of Fe can be reduced by the purification action of the pigment precursor of the reprecipitation method described above. Therefore, the content of Fe in the pigment fine particles can be lowered to 35 ppm or less. More preferably, it is pressed down to 30 ppm or less, and more preferably it is pressed down to 20 ppm or less.

[Example of manufacturing device]

Here, for the above, it can be close. The fluid processing apparatus for separating the processing surfaces for relative rotation will be briefly described with reference to Figs. 1 to 3 . This device is the same as the device described in Patent Document 7.

In Fig. 1, U indicates the upper side and S indicates the lower side. However, in the present invention, the up, down, front, rear, left and right directions indicate the relative positional relationship, and the absolute position is not limited. In Fig. 2 (A) and Fig. 3 (B), R represents a rotation direction. In Fig. 3(B), C indicates the direction of the centrifugal force (radial direction).

The fluid processing apparatus includes two processing units 10 and 20 that are opposed to each of the first and second processing units, and at least one of the processing units rotates. The surfaces facing the two processing members 10 and 20 are treated surfaces, respectively. The first processing member 10 includes the first processing surface 1 , and the second processing member 20 includes the second processing surface 2 .

Two processing surfaces 1, 2 and fluid (ie, the above pigments are dissolved The solution is connected to the flow path of the above-mentioned weak solvent to form a part of the flow path of the fluid to be treated. The interval between the two processing surfaces 1 and 2 can be appropriately changed, but is usually adjusted to be 1 mm or less, for example, a minute interval of about 0.1 μm to 50 μm. Thereby, the fluid to be processed between the two processing surfaces 1 and 2 becomes a forced film fluid forced by the two processing surfaces 1 and 2.

In the case where a plurality of fluids are treated by the apparatus, the apparatus is connected to the flow path of the first fluid to form a part of the flow path of the first fluid. Further, this device forms a part of the flow path of the second fluid different from the first fluid. Further, in this apparatus, the two flow paths are merged, and the two fluids are mixed and reacted between the processing surfaces 1 and 2 to perform fluid processing for depositing the fine particles.

Specifically, the device includes a first fixing bracket 11 that holds the first processing unit 10, a second fixing bracket 21 that holds the second processing unit 20, a junction pressure applying mechanism, a rotation driving mechanism, and The first introduction portion d1, the second introduction portion d2, and the fluid pressure applying mechanism p.

As shown in Fig. 2(A), in this embodiment, the first processing member 10 is an annular body, and more specifically, it is an annular disk. Further, the second processing member 20 is also an annular disk. In the embodiment, the first and second processing surfaces 1 and 2 that face the processing units 10 and 20 are mirror-polished, and the arithmetic mean roughness is not particularly limited, but is preferably 0.01 to 1.0 μm, more preferably It is 0.03~0.3μm.

Among the first fixing bracket 11 and the second fixing bracket 21, The one of the fixed brackets may be a rotary drive mechanism (not shown) such as a motor, and the other fixed bracket may be relatively rotated.

In this embodiment, the second fixing bracket 21 is fixed to the device, and is attached to the first fixing bracket 11 fixed to the rotating shaft 50 of the rotation driving mechanism of the same device, and is rotated by the first fixing bracket 11 The first processing member 10 that is supported is rotated with respect to the second processing member 20. Of course, the second processing member 20 may be rotated or both may be rotated.

In this embodiment, the second processing member 20 is close to the direction of the rotating shaft 50 with respect to the first processing member 10. In the accommodating portion 41 provided in the second fixing bracket 21, the detachable portion can be detachably accommodated on the side opposite to the processing surface 2 side of the second processing member 20. However, the first processing member 10 may be closer to or separated from the second processing member 20 than the second processing member 20, and the two processing members 10 and 20 may be separated from each other.

The accommodating portion 41 is a recess that accommodates a portion of the second processing member 20 on the side opposite to the processing surface 2 side, and forms an annular groove. The accommodating portion 41 has a sufficient gap that allows the portion on the side opposite to the processing surface 2 side of the second processing member 20 to be vaguely present, and accommodates the second processing member 20. The second processing member 20 can be arranged to move only in parallel in the axial direction. However, by increasing the gap, the second processing member 20 can tilt and shift the center line of the processing unit 20 with respect to the housing portion 41. The damage is parallel to the axial direction of the accommodating portion 41, and the center line of the second processing member 20 and the center line of the accommodating portion 41 may be radially offset. Off, displacement. In this manner, it is preferable to hold the second processing member 20 by holding the floating mechanism capable of three-dimensional displacement.

The flow system is introduced between the processing surfaces 1 and 2 from the first introduction portion d1 and the second introduction portion d2 in a state where the pressure is applied to the fluid pressure applying mechanism p constituted by the pump or the position energy. In the first embodiment, the first introduction portion d1 is a passage provided in the center of the annular second fixing bracket 21, and one end thereof is introduced into the processing surfaces 1 from the inside of the annular processing members 10 and 20. 2 rooms. The second introduction unit d2 supplies the second fluid that is in contact with the first fluid to the processing surfaces 1 and 2. In the second embodiment, the second introduction portion d2 is a passage provided inside the second processing member 20, and one end thereof is formed in the opening portion d20 of the second processing surface 2.

The first fluid pressurized by the fluid pressure applying means p is introduced into the space inside the processing portions 10 and 20 by the first introduction portion d1, and passes through the first processing surface 1 and the second processing surface 2 Between the two, the outer sides of the processing portions 10, 20 are passed.

Between the processing surfaces 1 and 2, the second fluid pressurized by the fluid pressure applying mechanism p is supplied from the second introduction portion d2, and merges with the first fluid, and the pigment solution is mixed by the two fluids. The precipitation reaction with the above-mentioned weak solvent precipitates the organic pigment fine particles, and the fluid containing the organic pigment fine particles is discharged to the outside of the two processing members 10 and 20 by the two processing surfaces 1 and 2.

The junction pressure applying mechanism applies a force acting in a direction close to the first processing surface 1 and the second processing surface 2 to the processing portion. In this embodiment, the junction pressure applying mechanism is disposed on the second fixed bracket In the rack 21, the second processing unit 20 is energized to the first processing unit 10.

The junction pressure applying means is for generating a force in a direction in which the first processing surface 1 of the first processing member 10 and the second processing surface 2 of the second processing member 20 are close to each other (hereinafter referred to as a junction). Pressure) of the institution. By the contact pressure and the equalization of the force separating the processing surfaces 1 and 2 by the fluid pressure, the interval between the two processing surfaces 1 and 2 is maintained at a specific minute interval, resulting in nm units to μm. A thin film fluid with a small film thickness. The junction pressure may be other pressures such as a magnetic force or a gravity, in addition to the elastic force of the spring 43 and the pressure of the energizing fluid such as air or oil introduced into the energizing fluid introduction portion 44.

In response to the energization of the junction pressure applying mechanism, the second processing member 20 is separated from the first processing member 10 by the separation force generated by the pressure, viscosity, and the like of the fluid pressurized by the fluid pressure applying mechanism p. A small interval is opened between the processing surfaces. In this manner, the distance between the first processing surface 1 and the second processing surface 2 is set with an accuracy of μm in accordance with the balance between the junction pressure and the separation force.

In addition to the fluid pressure or viscosity of the fluid, the separation force may be a centrifugal force formed by the rotation of the processing portion, a negative pressure when the negative pressure is applied to the energizing fluid introduction portion 44, and the spring 43 is stretched. The elasticity of the time. The joint pressure applying means may be provided not in the second processing member 20 but in the first processing member 10 or in both of them.

As shown in FIG. 2, the first processing surface 1 of the first processing member 10 can be formed from the center side of the first processing member 10 to the outside. That is, the groove-shaped recess 13 extending in the radial direction is implemented. As shown in FIG. 2(B), the planar shape of the concave portion 13 may be such that the first processing surface 1 is curved or spiral. Further, the concave portion 13 may be formed on the second processing surface 2 or may be formed on both the first and second processing surfaces 1 and 2. By forming such a concave portion 13, a micro-pump effect can be obtained, and there is an effect of attracting a fluid between the first and second processing surfaces 1 and 2.

It is preferable that the base end of the concave portion 13 reaches the inner circumference of the first processing member 10. The front end of the concave portion 13 is extended toward the outer peripheral surface side of the first processing member surface 1, and the depth thereof gradually decreases from the proximal end to the distal end.

A flat surface 16 having no recess 13 is provided between the front end of the recess 13 and the outer peripheral surface of the first processing surface 1.

It is preferable that the opening d20 is provided at a position facing the flat surface 16 of the first processing surface 1.

In particular, it is disposed on the downstream side (in this case, the outer side) of the flow direction when the micro-pump effect is introduced, compared with the spiral formed between the processing surfaces and converted into the flow direction of the laminar flow. The position of the flat surface 16 is preferably opposite.

Specifically, in FIG. 2(B), it is preferable that the distance n in the radial direction is set to be about 0.5 mm or more from the tip end of the concave portion 13 provided on the first processing surface 1. Thereby, under laminar flow conditions, mixing of a plurality of fluids and precipitation of fine particles can be performed.

The shape of the opening d20 may be a circular shape as shown by a broken line in FIG. 2(B) or a winding as shown in FIG. 2(B) or FIG. 3(B). A concentric circular ring shape of the central opening of the processing surface 2 of the annular disk.

In order to easily obtain the pigment fine particles having the crystallite size and the primary particle diameter of the present invention, the shape of the opening d20 is preferably a concentric circular ring shape of the central opening of the winding processing surface 2. It is presumed that the two fluids are in rapid contact, and the concentration distribution of the two fluids in the reaction field between the surfaces for the treatment is suppressed, and the mixed state becomes more uniform, so that the progress of the precipitation reaction becomes more uniform, and the obtained pigment microparticles have their crystallite size and primary particles. The path becomes more uniform.

The second introduction portion d2 may have directivity. For example, as shown in FIG. 3(A), the introduction direction of the opening d20 of the second processing surface 2 is inclined at a specific elevation angle (θ1) with respect to the second processing surface 2. The elevation angle (θ1) is set to be more than 0 degrees and less than 90 degrees, and in the case of a reaction having a fast reaction rate, it is preferably 1 degree or more and 45 degrees or less.

In addition, as shown in FIG. 3(B), the direction of introduction from the opening d20 of the second processing surface 2 is directional in the plane along the second processing surface 2. The introduction direction of the second fluid is a component in the radial direction of the processing surface, which is away from the center, and is positive in the component of the rotation direction of the fluid with respect to the processing surface for rotation. In other words, the line passing through the radial direction of the opening d20, that is, the outer direction, is divided into the reference line g, and has a specific angle (θ2) from the reference line g to the rotational direction R. Regarding this angle (θ2), it is preferable to exceed 0 degrees and not to reach 90 degrees.

This angle (θ2) can be changed in accordance with various conditions such as the reaction speed, the viscosity, and the rotational speed of the processing surface. In addition, the second The introduction portion d2 may also have no directivity at all.

The number of the above-described flow paths is two in the example of Fig. 1, but three or more may be used. In the example of FIG. 1, the second fluid is introduced between the processing surfaces 1 and 2 from the second introduction portion d2. However, the introduction portion may be provided in the first processing member 10 or both. Further, a plurality of introduction portions can be prepared for one type of fluid. In addition, the shape, size, or number of the openings for introduction of the respective processing members are not particularly limited, and can be appropriately changed. In addition, an opening for introduction may be provided immediately before or upstream of the first and second processing surfaces 1 and 2.

By controlling the ratio of crystallite size to crystallite size by the above-described manufacturing method and reaction apparatus, various parameters such as temperature, distance between treatment surfaces, supply and discharge of fluid can be controlled by controlling the reaction coefficient of the reaction field. The speed, etc., is fed back from the crystallite size of the obtained pigment particles, and the optimum value for each device is selected.

[Pigment Dispersion]

In the present invention, the diketopyrrolopyrrole pigment fine particles of the present invention described above are placed in an organic solvent of a dispersion medium to carry out dispersion treatment to obtain a pigment dispersion. The organic solvent is usually an ester-based organic solvent. Here, the ester-based organic solvent to be used is not particularly limited, and a boiling point is preferably 100 ° C or higher, more preferably 110 ° C or higher, and still more preferably 130 ° C or higher. Examples of such a high-boiling organic solvent include ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, and B. Glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, diethylene glycol monomethyl Ethyl acetate, diethylene glycol monobutyl ether acetate (BCA), and the like.

Among the above-mentioned ester-based organic solvents, propylene glycol monomethyl ether acetate (PGMEA, boiling point: 146 ° C) and propylene glycol monomethyl ether (PGME, boiling point: 120 ° C) are more preferable from the viewpoint of dispersibility of the organic pigment. . These ester organic solvents may be used singly or in combination of two or more.

Further, a dispersing agent may be added as necessary. The dispersing agent is not particularly limited. For example, when it is mainly an organic solvent system, for example, a carboxylic acid ester such as a polyurethane or a polyacrylate, a polyunsaturated polyamine or a polycarboxylic acid (partial) amine salt, Polycarboxylate ammonium salt, polycarboxylic acid alkylamine salt, polyoxyalkylene oxide, long chain polyamine guanamine phosphate, hydroxyl group-containing polycarboxylate or the like, poly(lower alkylene) Amine or a salt thereof formed by reacting a polyester with a polyester having a free carboxylic acid group; and when it is mainly aqueous, for example, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-( a water-soluble resin or a water-soluble polymer compound such as a methyl acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol or a polyvinyl pyrrolidone; a sodium lauryl sulfate or a polyoxyethylene alkyl ether Sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, dodecyl sulfate Monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, ten Sodium alkyl sulfate, styrene - acrylic acid copolymer of monoethanolamine, polyoxyethylene alkyl ether phosphate anions, etc. Surfactant; polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol single a nonionic surfactant such as lauric acid ester; an amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as alkyldimethylaminoacetic acid betaine; these may be used alone or in combination. Used above.

Among these, a dispersant having an amine structure in particular is excellent in dispersibility and is suitable for use. Examples of the dispersant having an amine structure include, for example, the Solsperse series manufactured by Lubrizol Co., Ltd., the Disperbyk series manufactured by BYK-Chemie Co., Ltd., the Efka series manufactured by BASF Corporation, and the AJISPER series manufactured by Ajinomoto Fine-Tech Co., Ltd., and the like. The amount of the dispersing agent is usually 100 parts by weight or less, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less based on 100 parts by weight of the pigment.

Further, a binder resin may be added simultaneously with the dispersant. Examples of the binder resin include a phenol resin, an alkyd resin, a polyester resin, an amine resin, a urea resin, a melamine resin, a guanamine resin, an epoxy resin, a styrene resin, a vinyl resin, a vinyl chloride resin, and a vinyl chloride/ Vinyl acetate copolymer resin, acrylic resin, polyurethane resin, oxime resin, polyamide resin, polyimide resin, rubber resin, cyclized rubber, maleinization oil resin A butyral resin, a polybutadiene resin, a cellulose resin, a chlorinated polyethylene, a chlorinated polypropylene, or the like. These binder resins may be used singly or in combination of two or more. The binder resin can also be added when a photosensitive coloring composition is obtained as described later.

Further, a compound such as a known pigment derivative may be added as necessary. These compounds are compounds of a secondary pigment and a dispersing agent, which are physically, electrically, and chemically adsorbed between the surface of the pigment and the dispersing agent, and have a function of improving dispersion stability. Examples of such a pigment derivative include diketopyrrolopyrrole, anthraquinone, phthalocyanine, metal phthalocyanine, quinacridone, azo chelate, azo, and isoindole. a ketone ketone, a pyranthrone, an indanthrone, an anthracycline, an anthanthrone, a flavanthrone, an anthraquinone, an anthrone An organic pigment such as a quinophthalone, a thioindole or a dioxazine is used as a precursor, and a pigment derived from a substituent such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbonium amide group or a sulfonylamino group is introduced. Things. The compounds such as the pigment derivative may be used singly or in combination of two or more.

The addition of such a dispersing agent or a compound such as a binder resin or a pigment derivative to the pigment dispersion contributes to reduction of flocculation, improvement of dispersion stability of the pigment, and improvement of viscosity characteristics of the dispersion.

The dispersion treatment is not limited to the disperser used in the method or the treatment, but by adjusting the stirring speed, the treatment time, and the like at the time of the treatment, even if the pigment fine particles of the present invention are not supplied with energy such as excessive flushing force, they may be dispersed. deal with. Therefore, it is also possible to use a stirring mechanism such as a ball mill, a bead mill, a sand mill or the like to vigorously stir a medium composed of glass, steel, stainless steel, ceramics, zirconium, zirconium dioxide or the like to cause a processed object. Disperser, but even if it is not accompanied by the pulverizer of the pigment particles Conditions can also be implemented. Further, the dispersion treatment may be carried out by using a disperser which does not use the above medium. In this case, the same apparatus as that used for the preparation of the pigment solution or the weak solvent may be mentioned. When the pulverizer of the pigment granules is not pulverized, the pulverization of the pigment granules can be reduced, and the uniformity of the pigment granules after the dispersion treatment can be improved. As a result, it is advantageous to easily obtain an effect of improving color characteristics and the like.

[Photosensitive coloring composition]

In the above pigment dispersion, at least a monomer and a photopolymerization initiator are mixed to obtain a photosensitive coloring composition.

The monomer is not particularly limited, and examples thereof include, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl group. In addition to monofunctional monomers of acrylate and N-vinylpyrrolidone, there are also tripropylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate and bisphenol A. A difunctional monomer of a diacrylate such as trimethylolpropane triacrylate and a trifunctional monomer of pentaerythritol triacrylate, other polyfunctional monomers such as dipentaerythritol penta and hexaacrylate, and the like. Two or more types of these photopolymerizable monomers can also be used.

The photopolymerization initiator may, for example, be an aromatic ketone, a triaryl imidazole dimer, a benzoin, a benzoin ether, an acetophenone, a benzophenone, a thioxanthone or an acetal ( Kttal), anthracene, triazines, imidazoles, oximes, phosphines, borates, carbazoles, titanocenes, polyhalogens, and the like. Preferably, for example, 4,4'-bis(diethylamino)di Combination of benzophenone with 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 4-[pN,N-bis(ethoxycarbonylmethyl)-2,6-di (Trichloromethyl)-s-triazine], 2-methyl-4'-(methylthio)-2-morpholinylpropiophenone. These photopolymerization initiators may be used singly or in combination of two or more kinds in any ratio as necessary.

Other, the alkali-soluble resin shown below may also be contained in the coloring composition.

The alkali-soluble resin can be used generally for a negative-type resist, and is not particularly limited as long as it is soluble in an aqueous alkali solution. For example, it is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (A) Acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n- Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-fluorenyl (meth) acrylate, benzyl (meth) acrylate And one or more selected from the group consisting of styrene, γ-methylstyrene, N-vinyl-2-pyrrolidone, and epoxypropyl (meth)acrylate, and selected from (meth)acrylic acid and itaconic acid. A copolymer composed of one or more of crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and the like, and an ethylenic unsaturated compound having a glycidyl group or a hydroxyl group may also be mentioned. A polymer or the like which forms the above copolymer. These alkali-soluble resins can also be added at the time of obtaining the pigment dispersion as described above.

The photosensitive coloring composition of the present invention may further contain a filling Additives such as agents, adhesion promoters, antioxidants, ultraviolet absorbers, and flat agents.

[Color Filter]

The photosensitive colored composition containing the fine particles of the pigment of the present invention described above is applied onto a substrate, photocured and developed to obtain a coating film, and a color filter can be produced. This step is referred to as a prebaking step. The photosensitive coloring composition is applied onto a substrate on a glass substrate or a ruthenium substrate, and a roll coater, a slit coater, a spray, a coating bar, and an applicator are used. It is preferable to use an applicator, a spin coater, a dip coater, an inkjet, or a screen printing. After the application, heating is preferably carried out from the viewpoint of drying the organic solvent, smoothness of the coating film, or handling. The heating temperature is preferably from 50 to 140 ° C, more preferably from 70 to 90 ° C, and the heating time is preferably from 0.5 to 60 minutes, more preferably from 1 to 10 minutes.

The light curing system irradiates the coating film with ultraviolet rays to harden the coating film. The photocuring is carried out in order to develop the pattern to remain on the glass substrate in the subsequent development, and it is preferable that the mask for preventing ultraviolet rays is not cured in the portion removed by development. It is preferred that the photocuring ultraviolet irradiation amount is in the range of 10 to 100 mJ/cm ² . The developing system immerses the hardened coating film after photohardening in an aqueous alkali solution, and then rinses with water to remove the unhardened portion. The alkali aqueous solution to be used preferably has a concentration of the alkali agent of 0.001 to 10% by weight, more preferably 0.01 to 1% by weight. Further, the alkali agent used for development is preferably an aqueous solution of ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, triethylamine, triethanolamine or tetramethylammonium hydroxide.

The film thickness of the coating film can be adjusted according to the desired color. Because the chromaticity also depends on the film thickness.

The developed coating film was heated to 200 to 300 ° C to obtain a cured film. Hereinafter, this step is referred to as a post-baking step. By heating the developed coating film, a cured film excellent in hardness can be formed. From the viewpoint of obtaining a cured film excellent in hardness and excellent in heat resistance, the heating temperature is preferably 200 to 300 °C. From the viewpoint of obtaining a cured film excellent in hardness and excellent in heat resistance, the heating time is preferably from 10 to 300 minutes. Preheating at 80~100°C for 10~60 minutes can also be carried out before the post-baking step.

Example

Hereinafter, the present invention will be described in more detail with reference to the embodiments, but the invention is not limited to the embodiments.

Further, the symbols in the following embodiments represent the following contents. Further, the following weight % is described as wt%.

DMSO: dimethyl hydrazine, NMP: N-methylpyrrolidone, TMAH aq.: 25 wt% aqueous solution of tetramethylammonium hydroxide, BTMA soln.: 40 wt% benzyltrimethylammonium hydroxide in methanol, EG: B Glycol, MeOH: methanol.

(Manufacture of brominated diketopyrrolopyrrole)

1. In a stainless steel reaction vessel with an alkali metal salt of a diketopyrrolopyrrole pigment compound formed in a reflux tube, a molecule is added under a nitrogen atmosphere. 200 parts of tert-pentyl alcohol and 140 parts of tert-pentoxide sodium which were dehydrated by a molecular sieve were heated to 100 ° C with stirring to prepare an alkoxide solution. Next, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were placed in a glass flask, and the mixture was heated to 90 ° C with stirring to dissolve, and the mixture solution was prepared. The heated solution of this mixture was vigorously stirred, and it was slowly dropped at a constant rate for 2 hours to the above alkoxide solution heated to 100 °C. After the completion of the dropwise addition, heating and stirring were continued at 90 ° C for 2 hours to obtain an alkali metal salt solution of a diketopyrrolopyrrole pigment compound.

2. Formation of red suspension

Further, 600 parts of methanol, 600 parts of water, and 114 parts of acetic acid were placed in a glass jacketed reaction vessel, and cooled to -10 °C. The cooled mixture was subjected to a high-speed stirring disperser (DISPERSER), and an alkali metal of a previously obtained diketopyrrolopyrrole pigment compound cooled to 75 ° C was added thereto while rotating a distribution disk having a diameter of 8 cm at 4000 rpm. Salt solution. At this time, while cooling, the temperature of the mixture of methanol, acetic acid, and water is often maintained at a temperature of -5 ° C or lower, and the addition rate of the alkali metal salt solution of the diketopyrrolopyrrole pigment compound at 75 ° C is adjusted. , add a small amount each time for about 120 minutes. After the addition of the alkali metal salt solution, red crystals were precipitated to obtain a red suspension.

3. Separation of brominated diketopyrrolopyrrole

Next, the obtained red suspension was loaded at 5 ° C with critical filtration. Set the filter to get the red paste. This paste was redispersed in 3500 parts of water at 25 ° C, washed, and subjected to filtration by a critical filtration apparatus for 3 times. The obtained water-paste of the diketopyrrolopyrrole pigment compound was dried at 60 ° C for 72 hours, and the brominated diketopyrrolopyrrole represented by the formula (III) which is a pigment precursor was obtained by pulverization (hereinafter referred to as "Bromide DPP" (150.8 parts by primary particle diameter of 40 to 60 nm observed by STEM described later).

Example 1 Pigment microparticles (modulation of pigment solution)

As 60% by weight of DMSO of the raw material 1 which is the solvent of the substrate in Table 2, TMAH aq. 28 wt% of the raw material 2, 9 wt% of the brominated DPP, and EG 3 wt% of the raw material 4 were added, and a high-speed rotary emulsification disperser (m) was used. -Technique Co., Ltd., product name: CLEARMIX, below CLEARMIX) Stirring to dissolve brominated DPP. The prescription and preparation conditions are shown in Table 2 together with other examples and comparative examples.

(modulation of weak solvent)

In 70 wt% of tap water of the raw material 1 in Table 3 as a weak solvent, 20 wt% of citric acid of the raw material 2 and 10 wt% of EG of the raw material 4 were mixed, and the weak solvent was mixed and mixed using CLEARMIX. The prescription and preparation conditions are shown in Table 3 together with other examples and comparative examples.

(precipitation of pigment particles)

It can be placed close to the opposite direction. At least one of the separations is uniformly diffused in the film fluid formed between the processing surfaces 1 and 2 that are rotated relative to the other. Stir. The mixed reaction apparatus mixes the prepared pigment solution and the weak solvent to continuously carry out a precipitation reaction in the film fluid. Specifically, a weak solvent as the first fluid is transported from the center (first introduction portion d1) of the apparatus shown in FIG. 1, and the pigment solution is introduced into the processing surface 1 as the second fluid by the second introduction portion d2. 2 rooms. The first fluid and the second fluid are mixed in the film fluid, and the fine particles of the pigment dissolved in the pigment solution are precipitated, and the pigment fine particle dispersion is spit from the processing surfaces 1 and 2 Out. The supply pressure of the first fluid and the second fluid, the liquid supply flow rate and the liquid supply temperature, and the number of rotations of the processing unit 10 (hereinafter referred to as the number of revolutions), the back pressure, and the temperature of the discharge liquid are used as the production conditions of the pigment fine particles, and Other examples and comparative examples are shown in Table 4. The temperature at which the first fluid and the second fluid are fed is measured before the introduction of the device (more specifically, before the introduction of the processing surfaces 1 and 2), and the temperature of the discharge fluid is measured. The temperature of the pigment fine particle dispersion liquid discharged from the processing surfaces 1 and 2 is measured. In addition, the opening d20 of the second introduction portion d2 is a concentric circular ring shape in which the central opening of the winding processing surface 2 is indicated by a broken line in FIG. 2(B).

(washing. Drying)

(a) In the pigment fine particle dispersion liquid discharged from the processing surfaces 1 and 2, the pigment fine particles are gradually agglomerated in order to separate only the pigment fine particles, and the pigment fine particles are collected by filtration under reduced pressure filtration (-0.1 MPaG) using a filter paper.

(b) The resulting wet cake of pigment microparticles was placed in 5 L of tap water and stirred at 6000 rpm using CLEARMIX. After washing for 1.5 minutes, the operation of recovering the washed liquid by vacuum filtration again was repeated four times to obtain a wet cake of pigment fine particles. The wet cake of the obtained pigment fine particles was vacuum dried to obtain a dry powder of pigment fine particles. The vacuum drying was carried out at 30 ° C, -0.10 MPaG for 72 hours.

X-ray diffraction measurement was performed on a dry powder of the obtained pigment fine particles by a multipurpose X-ray diffraction apparatus X'PertPowder (manufactured by PANalytical Co., Ltd.) using a data analysis software HighScorePlus Ver. 3.0e (3.0.5) (manufactured by PANalytical Co., Ltd.) ) for analysis. Further, quantitative analysis of ICP was carried out to measure the amount of Fe contained in the pigment fine particles.

Modulation of pigment dispersion

10 parts by weight of the dry powder of the obtained pigment fine particles, and "BYKLPN 6919" (manufactured by BYK-Chemie Co., Ltd.) as a dispersing agent, the solid content of 5 parts by weight, and CIpigment red 254 as a dispersing aid (hereinafter referred to as " 1 part by weight of sulfonated derivative of R254") and 70 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") as a solvent, and mixing and mixing using a paint mixer (manufactured by Asada Iron Works Co., Ltd.) The dispersion treatment was carried out in an hour to obtain a pigment dispersion of brominated DPP. The viscosity of the resulting pigment dispersion was measured. Further, the obtained pigment dispersion was diluted with PGMEA as a dispersion for STEM observation. The obtained dispersion for STEM observation was dropped onto a cotton film, and STEM observation was performed.

Further, in order to adjust the chromaticity, a pigment dispersion of C.I. pigment red 177 (hereinafter referred to as "R177") was prepared. In the pigment dispersion system of R177, 10 parts by weight of "CHROMOFINE RED A3B" (manufactured by BASF Corporation) as a pigment, and "BYKLPN6919" (manufactured by BYK-Chemie Co., Ltd.) as a dispersing agent, the solid content is 5 parts by weight, and it is used as a dispersing aid. The composition of 1 part by weight of the sulfonated derivative of R177 and 70 parts by weight of PGMEA as a solvent was prepared in the same manner as in the preparation of the above pigment dispersion of brominated DPP.

Production of photosensitive coloring composition

Regarding the pigment dispersion of brominated DPP and the pigment dispersion of R177, each of the photosensitive coloring compositions was produced by the following production method. 50 parts by weight of the pigment dispersion, 6 parts by weight of an acrylic resin ("ZAH-110" manufactured by Soken Chemical Co., Ltd.), and 4 parts by weight of dipentaerythritol hexaacrylate as a polymerizable monomer, as a photopolymerization initiator 2 1 part by weight of methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one ("IRGACURE 907" manufactured by BASF Corporation), and 100 parts by weight of PGMEA as a solvent were uniformly stirred and mixed. Filtration was carried out using a 1.0 μm filter to obtain a photosensitive coloring composition.

Production of hardened film

The following two types of hardened film systems were produced. A photosensitive coloring composition of brominated DPP was used, and in the post-baking step, a cured film having a chromaticity adjusted by chromaticity x = 0.6500 was prepared, and coarse particles, contrast, film thickness, and heat resistance were evaluated. Make A photosensitive coloring composition of brominated DPP and R177 was used, and in the post-baking step, a cured film having a chromaticity adjusted by chromaticity x = 0.6500 and y = 0.3230 was prepared, and the brightness was evaluated.

1. Pre-baking step

The photosensitive colored composition obtained above was applied onto a glass substrate by a spin coater, and then dried at 80 ° C for 3 minutes to obtain a coating film. A photomask was placed on the obtained coating film, and ultraviolet rays of 100 mJ/cm ^{2 were} irradiated using a UV fiber spot irradiation apparatus. Further, the mixture was shaken in an aqueous alkaline solution (0.04 wt% aqueous potassium hydroxide solution), followed by washing with pure water to remove the unhardened portion. Further, the number of rotations of the spin coater was changed so that the specified chromaticity was included, three coating films were produced, and the evaluation item of the specified chromaticity was calculated by the one-time correlation method.

2. Post-bake step

The coating film after removing the unhardened portion was subjected to preliminary heat treatment at 80 ° C for 30 minutes in a dryer, and then subjected to main heat treatment at 230 ° C for 30 minutes to obtain a cured film.

Example 2

A cured film was obtained in the same manner as in Example 1 except that the formulation of the pigment solution described in Table 2, the formulation of the weak solvent described in Table 3, and the conditions for the production of the pigment fine particles described in Table 4 were changed.

Example 3

A cured film was obtained in the same manner as in Example 1 except that the formulation of the weak solvent described in Table 3 was changed.

Example 4

A cured film was obtained in the same manner as in Example 1 except that the conditions for producing the fine particles of the particles described in Table 4 were changed.

Example 5

A cured film was obtained in the same manner as in Example 1 except that the formulation of the pigment solution described in Table 2 was changed.

Example 6

A cured film was obtained in the same manner as in Example 2 except that the formulation of the pigment solution described in Table 2 and the formulation of the weak solvent described in Table 3 were changed.

Comparative example 1

In the comparative example in which the pigment pulverization was not carried out, the brominated DPP used as the pigment precursor in Examples 1 to 6 was not subjected to pigment pulverization, and the pigment dispersion was prepared in the same manner as in Example 1, and the same was obtained in the following manner. membrane.

Comparative example 2

Comparative Example 2 describes the color characteristics, primary particle diameter, and change of the pigment fine particles produced by the pulverization. The production step of the fine particles of the pulverization method is carried out in accordance with the well-known Japanese Patent Publication No. 2013-82905.

50 parts by weight of brominated DPP, 550 parts by weight of sodium chloride, and 110 parts by weight of diethylene glycol were placed in a kneader, and kneaded by a salt grinding method at 50 ° C for 4 hours to prepare a pigment fine particle kneaded product.

In order to remove impurities from the obtained pigment fine particle kneaded material, the obtained kneaded material of the pigment fine particles was put into 5 L of tap water, and stirred at 6000 rpm for 15 minutes using CLEARMIX. After washing, the washed liquid was filtered under reduced pressure (-0.1 MPaG) using a filter paper, and the pigment fine particles were collected by filtration. The wet cake of the pigment microparticles collected by filtration was washed in the same manner as in Example 1. dry. Then, a pigment dispersion was prepared in the same manner as in Example 1, and a cured film was obtained in the same manner.

Comparative example 3

Using a burette, 350 mL of the pigment solution prepared in Example 2 was added at a rate of 35 mL/min. to 5 L of a weak solvent prepared in Example 2, which was stirred at 1700 rpm with CLEARMIX, to obtain a pigment fine particle dispersion. In order to separate the pigment fine particles by the pigment fine particle dispersion, the pigment fine particles are gradually agglomerated, and the pigment fine particles are collected by filtration under reduced pressure filtration (-0.1 MPaG) using a filter paper, and the wet cake of the collected and collected pigment fine particles is carried out. Example 1 is also washed. dry. Then, with In the same manner as in Example 1, a pigment dispersion was prepared, and in the same manner as below, a cured film was obtained.

Evaluation method

The crystallite size was measured by the aforementioned [measurement of crystallite size], and the ratio of the crystallite size was calculated. Moreover, the change rate of the surface interval is calculated by the above [the rate of change in the surface interval of the lattice plane]. Table 5 shows the results of these. Moreover, the X-ray diffraction pattern of brominated DPP is shown in Fig. 4. Compared with R254, the X-ray diffraction intensity is different, but the peak position appears in the same place, so it is assumed that the brominated DPP is the same as R254. The crystal lattice structure and the crystal lattice surface of the crystal structure are analyzed. As described above, the crystal structure of R254 is analyzed in the literature (Acta. Cryst. B49, 1056 (1993)) by X-ray crystal structure analysis, and the crystal structure is disclosed in the form of CIF data. When the crystal structure CIF data is used, the Bragg angle (2θ) can be made to correspond to the lattice plane of the crystal structure by calculating the software Mercury.

The amount of Fe was measured by qualitative analysis by ICP. The amount of Fe was measured using iCAP6300Duo manufactured by Thermo Fisher Scientific. The measurement results are shown in Table 5.

The obtained pigment dispersion was diluted 50-200 times with PGMEA, and treated with a ultrasonic homogenizer (manufactured by SND Corporation, ultrasonic cleaning machine US-105) for 5 minutes, and the particle image was observed. This observation was observed using an S-5200-shaped electric field release scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) at an observation magnification of 20 kV at an acceleration voltage of 1 million times, and the particles 100 which were clearly recognized by the observation image were observed. The long-diameter was measured using an image analysis software (Scandium manufactured by OLYMPUS) using SEM, and the standard deviation of the primary primary particle diameter and the primary particle diameter and the CV value of the primary particle diameter were calculated. The results and the viscosity of the pigment dispersion are shown in Table 5. In addition, when the obtained cured film was observed at 500 times by an optical microscope, the number of coarse particles and the color evaluation results (contrast, brightness, film thickness, and heat resistance) which can be visually confirmed are shown in Table 5. The value of the color evaluation shown in Table 5 was adjusted to x = 0.6500 and y = 0.3230 for the brightness, and the cured film adjusted to x = 0.6500 for the comparison, film thickness, and heat resistance was measured.

Among the measurement results shown in Table 5, for the number of coarse particles (number), it is judged that 0 to 19: ○, 20 to 59: △, 60 or more: ×, and 7000 or more for comparison judgment: ○, 5000 to 6999: Δ, 4999 or less: ×, the brightness is judged to be 18.90 or more: ○, 18.80 to 18.89: △, 18.79 or less: ×, and the film thickness (μm) is determined to be 2.400 or less: ○, 2.401 to 2.600: △, 2.601 or more: ×, for heat resistance (%) judged to be 22.9 or less: ○, 23.0 or more: ×, as shown in Table 5.

The above measurement results were all evaluated as ○, and the total evaluation was ○.

Examples 1 to 6 satisfying the (1 1 1) plane crystallite size of 140 Å or less, and the (1 5 -1) plane crystallite size of 80 Å or less, compared to the crystallite having the (1 1 1) plane When the size exceeds 140 Å, and the crystallite size of the (1 5 -1) plane exceeds the crystallite size of 80 Å, the results of comparison and brightness are obtained. This is because the crystallite size is controlled to be small, the area of the crystal grain boundary is made smaller, and the light scattering is reduced, so that the contrast and brightness of the resulting color filter are improved. Further, by forming primary particles with small crystallites, the primary particles are made smaller, the transmittance of the color filter is high, and light scattering is suppressed, which contributes to improvement of contrast and brightness.

The ratio of the crystallite size of the (1 1 1) plane to the (0 2 0) plane is in the range of 0.85 to 1.25, and the examples 1 to 6 having an average primary particle diameter of 5 to 40 nm are compared with the range having the range of 5 to 40 nm. When the ratio of the crystallite size and the average primary particle diameter were compared in Comparative Examples 1 to 3, the results of comparison and brightness were obtained. This is because the average primary particle size is small, the aspect ratio of the crystallites is small, and in the primary particles, the crystallites are easily arranged in such a manner that the anisotropy is less, and the primary particles become optically uniform. Improve contrast and brightness. Further, the primary particles composed of the nearly spherical crystallites have a small aspect ratio, are less likely to be aligned in the cured film, and have reduced anisotropy of the cured film, which also contributes to improvement in contrast and brightness. Further, since the aspect ratio of the primary particles is small, the specific surface area of the pigment fine particles formed by the primary particles is small, and the surface energy of the particles is small, so that the aggregation of the particles can be suppressed, even in the prior art, the viscosity is high, and the time is caused. A fine pigment which is viscous or has a possibility of causing gelation, but the brominated DPP pigment dispersion of the present invention can ensure dispersion stability.

Examples 1 to 6 in which the (0 2 0) plane of the crystal lattice has a rate of change of the surface spacing of 80 ° C and 230 ° C of 3.0% or less, compared with Comparative Example 1 in which the rate of change of the surface interval exceeds 3.0%. At 3 o'clock, a higher heat resistance result was obtained. This is because the brominated DPP having a small rate of change in the surface spacing due to the heating shown in the examples has a specific crystallite size or a specific crystallite size ratio, so that the crystal grain boundaries in the crystal structure can be suppressed to be small. The formation of crystallites is a tightly packed stable crystal structure, which can alleviate the contrast reduction caused by heating. As described above, by controlling the physical properties of the brominated DPP, it is possible to obtain brominated DPP pigment fine particles which satisfy the characteristics required for color filters such as contrast, brightness, and heat resistance at a high level.

Example 7 Pigment microparticles (modulation of pigment solution)

BTMA soln. 22.5 wt% of the raw material 2 was added to the DMSO 65.5 wt% of the raw material 1 as the solvent of the substrate in Table 6, and the raw material 3 was added. The commercially available pigment precursor R125 (having a primary particle diameter of 100 to 120 nm obtained by the above STEM observation) was 12 wt%, and the mixture was stirred with CLEARMIX to dissolve R254. The prescription and preparation conditions are shown in Table 6 together with other examples and comparative examples.

(modulation of weak solvent)

In 40 wt% of tap water of the raw material 1 in Table 7 as a weak solvent, 20 wt% of acetic acid of the raw material 2 and 40 wt% of MeOH of the raw material 3 were charged, and the weak solvent was mixed and mixed using CLEARMIX. The prescription and preparation conditions are shown in Table 7 together with other examples and comparative examples.

(precipitation of pigment particles)

It can be placed close to the opposite direction. At least one of the separations is uniformly diffused in the film fluid formed between the processing surfaces 1 and 2 that are rotated relative to the other. Stir. The mixed reaction apparatus mixes the prepared pigment solution and the weak solvent to continuously carry out a precipitation reaction in the film fluid. Specifically, a weak solvent as the first fluid is transported from the center (first introduction portion d1) of the apparatus shown in FIG. 1, and the pigment solution is introduced into the processing surface 1 as the second fluid by the second introduction portion d2. 2 rooms. The first fluid and the second fluid are mixed in the film fluid, and the fine particles of the pigment dissolved in the pigment solution are precipitated, and the pigment fine particle dispersion is discharged from the processing surfaces 1 and 2. The supply pressure of the first fluid and the second fluid, the liquid supply flow rate and the liquid supply temperature, and the number of rotations of the processing unit 10 (hereinafter referred to as the number of revolutions), the back pressure, and the temperature of the discharge liquid are used as the production conditions of the pigment fine particles, and Other examples and comparative examples are shown in Table 8. The temperature at which the first fluid and the second fluid are fed is measured before the introduction of the device (more specifically, before the introduction of the processing surfaces 1 and 2), and the temperature of the discharge fluid is measured. The temperature of the pigment fine particle dispersion liquid discharged from the processing surfaces 1 and 2 is measured. In addition, the opening d20 of the second introduction portion d2 is a concentric circular ring shape in which the central opening of the winding processing surface 2 is indicated by a broken line in FIG. 2(B).

(washing. Drying)

(a) In the pigment fine particle dispersion liquid discharged from the processing surfaces 1 and 2, the pigment fine particles are gradually agglomerated in order to separate and separate the pigment fine particles, and the fine particles are collected by filtration under reduced pressure filtration (-0.1 MPaG) using a filter paper.

(b) The resulting wet cake of pigment microparticles was placed in 5 L of tap water and stirred at 6000 rpm using CLEARMIX. After washing for 1.5 minutes, the operation of recovering the washed liquid by vacuum filtration again was repeated four times to obtain a wet cake of pigment fine particles. The wet cake of the obtained pigment fine particles was vacuum dried to obtain a dry powder of pigment fine particles. The vacuum drying was carried out at 30 ° C, -0.10 MPaG for 72 hours.

X-ray diffraction measurement was performed on a dry powder of the obtained pigment fine particles by a multipurpose X-ray diffraction apparatus X'PertPowder (manufactured by PANalytical Co., Ltd.) using a data analysis software HighScorePlus Ver. 3.0e (3.0.5) (manufactured by PANalytical Co., Ltd.) ) for analysis. Further, quantitative analysis of ICP was carried out to measure the amount of Fe contained in the pigment fine particles.

Modulation of pigment dispersion

10 parts by weight of the dry powder of the obtained pigment fine particles, and "BYKLPN 6919" (manufactured by BYK-Chemie Co., Ltd.) as a dispersing agent, a solid content of 5 parts by weight, and a sulfonated derivative of CIpigment red 254 as a dispersing aid 70 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") as a solvent, and a mixture of a paint mixer (manufactured by Asada Iron Works Co., Ltd.) for 6 hours, and a dispersion treatment was carried out to obtain R254. Pigment dispersion. Further, the obtained pigment dispersion was diluted with PGMEA to obtain a dispersion for STEM observation. The obtained dispersion for STEM observation was dropped onto a cotton film, and STEM observation was performed.

Further, in order to adjust the chromaticity, a pigment dispersion of R177 was prepared in the same manner as described above.

Production of photosensitive coloring composition

Regarding the pigment dispersion of R254 and the pigment dispersion of R177, the respective photosensitive coloring compositions were produced by the following production methods. 50 parts by weight of the pigment dispersion, 6 parts by weight of an acrylic resin ("ZAH-110" manufactured by Soken Chemical Co., Ltd.), and 4 parts by weight of dipentaerythritol hexaacrylate as a polymerizable monomer, as a photopolymerization initiator 2 1 part by weight of methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one ("IRGACURE 907" manufactured by BASF Corporation), and 100 parts by weight of PGMEA as a solvent were uniformly stirred and mixed. Filtration was carried out using a 1.0 μm filter to obtain a photosensitive coloring composition.

Production of hardened film

The following two types of hardened film systems were produced. When the photosensitive coloring composition of R254 was used, in the post-baking step, a cured film having a chromaticity adjusted by chromaticity x = 0.6500 was prepared, and coarse particles, contrast, film thickness, and heat resistance were evaluated. When the photosensitive coloring composition of R254 and R177 was used, in the post-baking step, a cured film having a chromaticity adjusted by chromaticity x = 0.6500 and y = 0.3230 was produced, and the brightness was evaluated.

1. Pre-baking step

The photosensitive colored composition obtained above was applied onto a glass substrate by a spin coater, and then dried at 80 ° C for 3 minutes to obtain a coating film. A photomask was placed on the obtained coating film, and ultraviolet rays of 100 mJ/cm ^{2 were} irradiated using a UV fiber spot irradiation apparatus. Further, the mixture was shaken in an aqueous alkaline solution (0.04 wt% aqueous potassium hydroxide solution), followed by washing with pure water to remove the unhardened portion. Further, the number of rotations of the spin coater was changed so that the specified chromaticity was included, three coating films were produced, and the evaluation item of the specified chromaticity was calculated by the one-time correlation method.

2. Post-bake step

The coating film after removing the unhardened portion was dried in a dryer at 80 ° C for 30 minutes, and then subjected to main heating treatment at 230 ° C for 30 minutes to obtain a cured film.

Example 8

A cured film was obtained in the same manner as in Example 7 except that the formulation of the pigment solution described in Table 6, the formulation of the weak solvent described in Table 7, and the conditions for the production of the pigment fine particles described in Table 8 were changed.

Example 9

A cured film was obtained in the same manner as in Example 8 except that the pigment dissolving liquid described in Table 6 and the pigment fine particle preparation conditions described in Table 8 were changed.

Comparative example 4

In the comparative example in which the pigment fine particles were not subjected to the pigment fine particles which were used as the pigment precursors in Examples 7 to 9, the pigment dispersion was prepared in the same manner as in Example 7, and a cured film was obtained in the same manner.

Comparative Example 5

A cured film was obtained in the same manner as in Example 9 except that the formulation of the weak solvent described in Table 7 and the conditions for the production of the pigment fine particles described in Table 8 were changed. Further, since only tap water as a weak solvent was used, the CLEARMIX-free weak solvent was not used.

Comparative Example 6

350 mL of the pigment solution prepared in Example 8 was added using a burette at a rate of 35 mL/min. and stirred at 1700 rpm using CLEARMIX. In 1.1 L of the weak solvent prepared in Example 8, a pigment fine particle dispersion was obtained. In order to separate the pigment fine particles by the pigment fine particle dispersion, the pigment fine particles are gradually agglomerated, and the pigment fine particles are collected by filtration under reduced pressure filtration (-0.1 MPaG) using a filter paper, and the wet cake of the collected and collected pigment fine particles is carried out. Example 7 is also washed. dry. Then, a pigment dispersion was prepared in the same manner as in Example 7, and a cured film was obtained in the same manner.

The evaluation methods were carried out in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 3. The results are shown in Table 9. Further, the determination was also performed in the same manner as in the judgments of Examples 1 to 6 and Comparative Examples 1 to 3.

Examples 7 to 9 satisfying the (1 1 1) plane crystallite size of 140 Å or less, and the (1 5 -1) plane crystallite size of 80 Å or less, compared to the crystallite having the (1 1 1) plane When the size exceeds 140 Å, and the crystallite size of the (1 5 -1) plane exceeds the crystallite size of 80 Å, the results of comparison and brightness are obtained. This is because the crystallite size is controlled to be small, the area of the crystal grain boundary is made smaller, and the light scattering is reduced, so that the contrast and brightness of the resulting color filter are improved. Further, by forming primary particles with small crystallites, the primary particles are made smaller, the transmittance of the color filter is high, and light scattering is suppressed, which contributes to improvement of contrast and brightness.

Examples 7 to 9 in which the ratio of the crystallite size of the (1 1 1) plane to the (0 2 0) plane is in the range of 0.85 to 1.25, and the average primary particle diameter is 5 to 40 nm, compared to the range having the range When the ratio of the crystallite size and the average primary particle diameter were compared in the comparative examples 4 to 6, the results of comparison and brightness were obtained. This is because the average primary particle size is small, and the aspect ratio of the crystallites is small. In the primary particles, the crystallites are easily arranged in such a manner that the anisotropy is less, and the primary particles become optically uniform, improving contrast and brightness. Further, the primary particles composed of the nearly spherical crystallites have a small aspect ratio, are less likely to be aligned in the cured film, and have reduced anisotropy of the cured film, which also contributes to improvement in contrast and brightness. Further, since the aspect ratio of the primary particles is small, the specific surface area of the pigment fine particles formed by the primary particles is small, and the surface energy of the particles is small, so that the aggregation of the particles can be suppressed, even in the prior art, the viscosity is high, and the time is caused. A fine pigment which is viscous or has a possibility of causing gelation, but the R254 pigment dispersion of the present invention can ensure dispersion stability.

The change of the surface spacing of the (0 2 0) plane of the crystal lattice at 80 ° C and 230 ° C In Examples 7 to 9 in which the rate was 3.0% or less, the results of higher heat resistance were obtained as compared with Comparative Examples 5 and 6 in which the rate of change of the surface interval exceeded 3.0%. This is because R254, which has a small rate of change in the surface spacing due to heating as shown in the examples, has a specific crystallite size or a specific crystallite size ratio, so that the crystal grain boundary in the crystal structure can be suppressed to be small and microscopically formed. The crystal is a tightly packed stable crystal structure, which can alleviate the contrast reduction caused by heating.

As described above, by controlling the physical properties of the diketopyrrolopyrrole pigment fine particles, it is possible to obtain red pigment fine particles which satisfy the characteristics required for color filters such as contrast, brightness, and heat resistance at a high level.

Claims (19)

A diketopyrrolopyrrole pigment microparticle containing 90% or more of a compound represented by the following general formula (I), which is calculated by a X-ray diffraction pattern (±1 ±1 ±1) Among the eight faces, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less. [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent]. A diketopyrrolopyrrole pigment microparticle containing a compound represented by the following general formula (I), which is 8 (±1 ±1 ±1) of a lattice plane calculated by an X-ray diffraction pattern In the plane, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less, and the crystallite size in the (1 5 -1) plane direction calculated by the X-ray diffraction pattern is Below 80Å, [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent]. a diketopyrrolopyrrole pigment microparticle containing a compound represented by the following general formula (I), which is calculated from 8 planes of (±1 ±1 ±1) calculated by an X-ray diffraction pattern, The size of the crystallite in the plane direction corresponding to the largest peak in the X-ray diffraction pattern, divided by the lattice plane calculated by the X-ray diffraction pattern, and the largest peak in 2θ=3~10° The ratio of the crystallite size calculated by the crystallite size of the corresponding surface direction is 0.85 to 1.25, and the average primary particle diameter is 5 to 40 nm. [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent]. A diketopyrrolopyrrole pigment microparticle containing 90% or more of a compound represented by the following general formula (I), which is a lattice corresponding to 2θ=24.5°±0.3° calculated by an X-ray diffraction pattern The crystallite size of the surface is below 140Å. In [the general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF _3, may have a substituent group of saturated or unsaturated alkyl of a group or an aryl group which may have a substituent]. A diketopyrrolopyrrole pigment microparticle containing 90% or more of a compound represented by the following general formula (I), which is a crystal corresponding to 2θ=24.5°±0.3° calculated by an X-ray diffraction pattern The crystallite size of the grid is 140 Å or less, and the crystallite size corresponding to 2θ=28.0°±0.3° calculated by the X-ray diffraction pattern is less than 80 Å. [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent]. For example, the ketopyrrolopyrrole pigment microparticles of the first, second, fourth or fifth aspect of the patent application have an average primary particle diameter of 5 to 40 nm. A diketopyrrolopyrrole pigment microparticle containing a compound represented by the following general formula (I), which is a lattice plane corresponding to 2θ=24.5°±0.3° calculated by an X-ray diffraction pattern The crystallite size is divided by the crystallite size of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern, and the ratio of the crystallite size is 0.85 to 1.25, and the average primary particle is obtained. The diameter is 5~40nm, [In the above general formula (I), X ₁ and X ₂ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkane which may have a substituent. a group or an aryl group which may have a substituent]. The diketopyrrolopyrrole pigment microparticles according to any one of claims 1 to 7, wherein the crystal lattice corresponding to the largest peak of 2θ=3 to 10° calculated by the X-ray diffraction pattern is obtained. The rate of change of the surface at 80 ° C and the value at 230 ° C (according to the following specific formula) is 3.0% or less, and the value at 80 ° C and the rate of change at 230 ° C = {(at 230 Interval at °C) / (interval at 80 °C) × 100} - 100 (%) [Specific formula] The diketopyrrolopyrrole pigment microparticles according to any one of claims 1 to 7, wherein the surface of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern is obtained. The value of the interval at 80 ° C and the rate of change at 230 ° C (according to the following specific formula) is 3.0% or less, and the value at 80 ° C and the rate of change at 230 ° C = {(in Surface spacing at 230 ° C) / (area spacing at 80 ° C) × 100} - 100 (%) [Specific formula] The diketopyrrolopyrrole pigment microparticles according to any one of claims 1 to 9, wherein the standard deviation of the primary particle diameter is less than 7.0. The diketopyrrolopyrrole pigment fine particles according to any one of claims 1 to 10, wherein a coefficient of variation (CV value) of the primary particle diameter is less than 30. The diketopyrrolopyrrole pigment fine particles according to any one of claims 1 to 11, wherein the content of Fe is 35 ppm or less. The diketopyrrolopyrrole pigment fine particles according to any one of the above items, wherein the general formula (I) is represented by the following general formula (II), [In the above general formula (II), R is independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, -CF ₃ , a saturated or unsaturated alkyl group which may have a substituent, or An aryl group which may have a substituent]. For example, in the ninth ketopyrrolopyrrole pigment microparticles of claim 13 wherein R is bromine represented by the following formula (III), A diketopyrrolopyrrole pigment microparticle containing a compound represented by the following formula (III), which is 8 (±1 ±1 ±1) of a lattice plane calculated by an X-ray diffraction pattern In the plane, the crystallite size corresponding to the largest peak in the X-ray diffraction pattern is 140 Å or less. A pigment dispersion which is a pigment dispersion containing at least an organic pigment and an organic solvent, wherein the organic pigment is a diketopyrrolopyrrole pigment fine particle according to any one of claims 1 to 15. A photosensitive coloring composition containing at least a diketopyrrolopyrrole pigment fine particle according to any one of claims 1 to 15. A color filter comprising at least a photosensitive coloring composition as claimed in claim 17 of the patent application. A color filter comprising at least a diketopyrrolopyrrole pigment fine particle according to any one of claims 1 to 15.