TW202108704A - 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 140 Å, 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 particles, pigment dispersions, photosensitive coloring compositions and color filters

The present invention relates to novel pigment particles and pigment dispersions, photosensitive coloring compositions and color filters using them.

Color filters used in liquid crystal display devices and solid-state image sensors. Generally speaking, color materials such as dyes or pigments are dissolved or dispersed in a solvent liquid, and a coloring composition such as a resin is applied to a glass substrate or a silicon substrate. After waiting, make the exposure. Manufactured in steps of hardening, developing, and thermal hardening. The durability of the color filter is related to the life of the liquid crystal display device and the solid-state image sensor. Therefore, the pigment dispersion method using pigments with excellent heat resistance or solvent resistance as the color material of the color composition is the mainstream. The pigment dispersion used here mainly uses a non-aqueous pigment dispersion in which the pigment is dispersed in an organic solvent. The primary particle size, dispersed particle size, crystallinity and other characteristics of the pigment particles contained in the dispersion are used for the color of the final product. The color characteristics, heat resistance and other performance of the filter have a great influence.

In recent years, color filters used in liquid crystal display devices and solid-state image sensors have been required to have high color enrichment and power saving. In order to reach For their purposes, the color characteristics of color filters are strongly required to have higher contrast, high brightness, and high tinting power.

The organic pigments used in the colorants for the red filter segment are generally made of diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, or bisazo-based pigments, which have excellent light resistance and heat resistance. Or they can be used in combination. However, these commercially available organic pigments have large and uneven primary particle sizes, so they cannot be used directly to achieve the color characteristics required by the color filter. Therefore, many attempts have been made to review the miniaturization of such organic pigments.

In particular, diketopyrrolopyrrole pigments are organic pigments with excellent brightness, so they have been used in recent years. Among them, CIpigment red 254 and brominated diketopyrrolopyrrole, especially organic pigments with excellent color characteristics, are actively reviewing the fineness (Hereinafter also referred to as "micronization").

For example, as described in Patent Documents 1 and 2, the so-called salt milling method, which uses inorganic salts such as sodium chloride as a medium, preliminarily mixes organic pigments and organic solvents, and pulverizes organic pigments by a kneader, may be as patented Document 3, Patent Document 4, or Patent Document 5 describes a so-called reprecipitation method in which a solution of an organic pigment dissolved in a good solvent is mixed with a weak solvent of an organic pigment compatible with the good solvent to generate pigment particles, or a combination such as the patent The reprecipitation method and the salt grinding method described in Document 6 are the methods for miniaturizing organic pigments.

In addition, it provides accessibility in the opposite arrangement as described in Patent Document 7. At least one of the separation is relative to the other, and is mixed and dissolved in the thin film fluid formed between at least two processing surfaces that rotate relative to each other. A manufacturing method for the pigment dissolving liquid of the pigment and the fine particles of the solvent for the precipitation of the organic pigment fine particles.

Prior art literature

Patent literature

Patent Document 1: JP 2012-211970 A

Patent Document 2: JP 2014-177532 A

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

Patent Document 4: Japanese Patent Application Publication No. 2011-137142

Patent Document 5: International Publication No. WO2011/024896 Pamphlet

Patent Document 6: Japanese Patent Application Publication No. 2015-102858

Patent Document 7: International Publication No. WO2011/096401 Pamphlet

Summary of the invention

By using organic pigment particles that have been miniaturized by applying these conventional technologies, it has a certain effect on the performance of high-contrast, high-brightness color filters. However, after review by the present inventors and others, those obtained by such conventional technologies cannot sufficiently meet the high contrast and high brightness required by color filters. In addition, in Patent Document 3 or Patent Document 5, due to the addition of color It is impossible to obtain organic pigment particles and other materials that can obtain color filters with high contrast and high tinting power that are strongly required in recent years. Dispersions.

The problem to be solved by the present invention is to provide high-contrast and high-brightness diketopyrrolopyrrole-based pigment particles. In the case of using a pigment dispersion containing the pigment particles, a good filter section is formed and has the necessary performance. A photosensitive coloring composition with an excellent balance of performance, and a high-color rich color filter that uses the contrast and excellent brightness.

As a result of careful research by the inventors, it was confirmed that the diketopyrrolopyrrole-based pigments mainly have crystal growth in three directions. Among them, it was found that the crystallite size in a specific crystal growth direction is below a certain value or relative to each crystal growth direction. , The specific crystallite size ratio is within a certain range of diketopyrrolopyrrole pigments, which have a fine and uniform primary particle size, with a high level and a good balance, to meet the above-mentioned characteristics required as a color filter.

The present invention solves the problem by the following means.

(1) A diketopyrrolopyrrole pigment microparticle containing 90% or more of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern in the crystal lattice plane (±1 ± Among the 8 planes of 1 ±1), the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is less than 140 Å,

[上述一般式(I)中，X₁及X₂各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、氰基、-CF₃、可具有取代基之飽和或不飽和之烷基、或可具有取代基之芳基]。

[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 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 X-ray diffraction pattern in the lattice plane (±1 ±1 ±1) Among the 8 planes, the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is less than 140Å. The size of the (1 5 -1) plane direction calculated by the X-ray diffraction pattern The crystal size is below 80Å.

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

(4) A diketopyrrolopyrrole pigment microparticle containing more than 90% 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 less than 140Å.

(5) A diketopyrrolopyrrole pigment microparticle containing more than 90% 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 lattice plane is less than 140Å, and the crystallite size of the lattice plane corresponding to 2θ=28.0°±0.3° calculated by the X-ray diffraction pattern is less than 80Å.

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

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

(8) The diketopyrrolopyrrole pigment particles of any one of items (1) to (7) above, wherein the maximum peak in 2θ=3~10° calculated by X-ray diffraction pattern The rate of change (according to the following specific formula) between the value at 80°C and the value at 230°C (based on the following specific formula) of the interplanar spacing of the corresponding lattice plane is less than 3.0%,

The rate of change between the value at 80℃ and the value at 230℃={(plane interval at 230℃)/(plane interval at 80℃)×100}-100(%)[specific formula].

(9) Diketopyrrolo as described in any one of items (1) to (7) above Pyrrole-based pigment particles, in which the rate of change between the value at 80°C and the value at 230°C between the interplanar spacing of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern ( According to the following specific formula) is below 3.0%,

The rate of change between the value at 80℃ and the value at 230℃={(plane interval at 230℃)/(plane interval at 80℃)×100}-100(%)[specific formula].

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

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

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

(13) The diketopyrrolopyrrole pigment microparticles according to any one of the above items (1) to (12), wherein the above general formula (I) is represented by the following general formula (II),

[上述一般式(II)中，R為各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、氰基、-CF₃、可具有取代 基之飽和或不飽和之烷基、或可具有取代基之芳基]。

[In the above general formula (II), R is each independently representing 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 diketopyrrolopyrrole pigment fine particles according to the above item (13), wherein R is bromine and represented by the following formula (III),

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

(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 items (1) to (15) above Microparticles.

(17) A photosensitive coloring composition containing at least diketopyrrolopyrrole pigment particles as described in any one of (1) to (15) above.

(18) A color filter containing at least the photosensitive coloring composition according to the above item (17).

(19) A color filter containing at least diketopyrrolopyrrole pigment particles as described in any one of items (1) to (15) above.

According to the present invention, it is possible to provide diketopyrrolopyrrole-based pigment particles having the characteristics of any one of (1) to (15) described above, a pigment dispersion containing the pigment particles, a photosensitive coloring composition, and a color Filter. By using the pigment fine particles, although they are fine particles, they can be easily dispersed. When the pigment dispersion containing the pigment fine particles is used, it can provide high contrast, high coloring power, and excellent heat resistance. It is very useful as a color filter. A photosensitive coloring composition with suitable performance and a color filter with excellent contrast and brightness using the photosensitive coloring composition.

[Fig. 1] is a schematic cross-sectional view of a fluid treatment device for implementing a fluid treatment method according to an embodiment of the present invention.

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

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

[Figure 4] is the X-ray diffraction pattern of brominated diketopyrrolopyrrole and C.I.pigment red 254.

[Figure 5] Obliquely viewed from above the surface of the aromatic ring in the crystal of brominated diketopyrrolopyrrole and C.I.pigment red 254 becomes zig zag) A schematic diagram of the zigzag in the laminated structure of herringbone.

[Fig. 6] is a schematic view of the zigzag in the laminated structure in which the aromatic ring in the crystal of brominated diketopyrrolopyrrole and C.I.pigment red 254 becomes zigzag zigzag pattern viewed laterally.

[Fig. 7] A schematic diagram showing the relationship between secondary particles, primary particles, crystallites, and crystal planes.

Form of invention

The preferred embodiments of the present invention are described below, but the present invention is not limited to these.

The diketopyrrolopyrrole pigment microparticles of the present invention have any one of the following characteristics (1) to (15).

(1) A diketopyrrolopyrrole pigment microparticle containing 90% or more of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern in the crystal lattice plane (±1 ± Among the 8 planes of 1 ±1), the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is less than 140 Å,

[上述一般式(I)中，X₁及X₂各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、氰基、-CF₃、可具有取代基之飽和或不飽和之烷基、或可具有取代基之芳基]。

[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 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 X-ray diffraction pattern in the lattice plane (±1 ±1 ±1) Among the 8 planes, the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is less than 140Å. The size of the (1 5 -1) plane direction calculated by the X-ray diffraction pattern The crystal size is below 80Å.

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

(4) A diketopyrrolopyrrole pigment microparticle containing more than 90% 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 lattice plane is less than 140Å.

(5) A diketopyrrolopyrrole pigment microparticle containing more than 90% 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 lattice plane is less than 140Å, calculated by X-ray diffraction pattern and 2θ=28.0°±0.3° The crystallite size of the corresponding lattice plane is less than 80Å.

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

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

(8) The diketopyrrolopyrrole pigment particles of any one of items (1) to (7) above, wherein the maximum peak in 2θ=3~10° calculated by X-ray diffraction pattern The rate of change (according to the following specific formula) between the value at 80°C and the value at 230°C (based on the following specific formula) of the interplanar spacing of the corresponding lattice plane is less than 3.0%,

The rate of change between the value at 80℃ and the value at 230℃={(plane interval at 230℃)/(plane interval at 80℃)×100}-100(%)[specific formula].

(9) The diketopyrrolopyrrole pigment particles of any one of items (1) to (7) above, wherein the crystal corresponding to 2θ=7.4°±0.3° calculated by X-ray diffraction pattern The rate of change (according to the following specific formula) between the value at 80°C and the value at 230°C (based on the following specific formula) of the surface interval of the grid surface is below 3.0%,

The rate of change between the value at 80℃ and the value at 230℃={(plane interval at 230℃)/(plane interval at 80℃)×100}-100(%) [Specific formula].

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

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

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

(13) The diketopyrrolopyrrole pigment microparticles according to any one of the above items (1) to (12), wherein the above general formula (I) is represented by the following general formula (II),

[上述一般式(II)中，R為各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、氰基、-CF₃、可具有取代基之飽和或不飽和之烷基、或可具有取代基之芳基]。

[In the above general formula (II), R is each independently representing 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 diketopyrrolopyrrole pigment fine particles according to the above item (13), wherein R is bromine and represented by the following formula (III),

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

(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 items (1) to (15) above Microparticles.

(17) A photosensitive coloring composition containing at least diketopyrrolopyrrole pigment particles as described in any one of (1) to (15) above.

(18) A color filter containing at least the photosensitive coloring composition according to the above item (17).

(19) A color filter containing at least diketopyrrolopyrrole pigment particles as described in any one of items (1) to (15) above.

According to the present invention, it is possible to provide a photosensitive coloring composition using diketopyrrolopyrrole-based pigment particles having any one of the above-mentioned characteristics (1) to (15), especially by using pigment particles containing these The color filter made of the photosensitive coloring composition obtained from the pigment dispersion The light sheet has high contrast, high tinting power, and excellent heat resistance, so it can provide photosensitive coloring composition and color filter with very suitable performance.

[Pigment species]

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

[上述一般式(I)中，X₁及X₂各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、氰基、-CF₃、可具有取代基之飽和或不飽和之烷基、或可具有取代基之芳基]

[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 Group or aryl group which may have substituent]

Such a diketopyrrolopyrrole-based pigment compound may be obtained by using various conventionally known production methods or various commercially available products, for example.

For example, the basic manufacturing method of a diketopyrrolopyrrole pigment compound is disclosed in USP 4,415,685, USP 4,579,949 and the basis for the corresponding patents described in the succinate synthesis method using a nitrile compound as a starting material. Method, select the type, number, and position of the functional group of the starting substance, and select the type, number, and position of X ₁ and X _{2 in} the above general formula (I). In addition, various methods of improvement include, for example, Japanese Patent Application Publication No. 58-210084, Japanese Patent Application Publication No. 07-90189, Japanese Patent Application Publication No. 08-48908, pamphlet WO2009/81930, EP1411092 B1 Publication, Japanese Obtained from the method described in JP 2012-211970 A, etc.

Color Index (C.I.) descriptions include, 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 commercially available products are also available.

Among these various diketopyrrolopyrrole pigment compounds represented by the general formula (I), in particular, the diketopyrrolopyrrole pigment compounds represented by the following general formula (II) having a substituent at the (para) position The compound, due to its excellent hue, is suitable for use as a red pigment.

[上述一般式(II)中，R各自獨立表示氫原子、氟原子、氯原子、溴原子、碘原子、氰基、-CF₃、可具有取代基之飽和或不飽和之烷基、或可具有取代基之芳基]

[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 that may have a substituent, or Substituent aryl]

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

C.I.pigment red 254 and brominated diketopyrrolopyrrole have different hues due to the different types of substituents. Compared with C.I.pigment red 254, the brominated diketopyrrolopyrrole shifts the splitting wavelength to the longer wavelength side, and becomes a more bluish red. To match the chromaticity of the purpose, you can choose to use these.

In particular, the brominated diketopyrrolopyrrole represented by the above formula (III) is due to the sterific hindrance of the bromine atom, and the intermolecular bond is weaker than that of CIpigment red 254, so it is easy to be microparticulate. Obtain the performance suitable for color filters with high contrast and high brightness, so it is better for color filters.

In addition, especially when using brominated diketopyrrolopyrrole to calculate the crystallite size or the crystallite size ratio of the present invention described below, the present inventors have learned 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 also contain organic pigments other than the diketopyrrolopyrrole pigment compound. In this way, other organic pigments can also be used for particle size control or chromaticity adjustment. The organic pigments that can be mixed and used at this time are not particularly limited. Examples include perylene-based pigments, perinone- based pigments, quinacridone-based pigments, quinacridone-quinone-based pigments, anthraquinone-based pigments, Anthraquinone pigments, benzimidazolone pigments, bisazo condensation pigments, bisazo pigments, azo pigments, indanthrone pigments, phthalocyanine pigments, triaryl carbon (carbonium) series Pigments, dioxazine-based pigments, aminoanthraquinone-based pigments, Thioindigo-based pigments, isoindoline-based pigments, isoindolinone-based pigments, pyranthrone-based pigments, isoviolanthracene Isoviolanthrone (Isoviolanthrone) is a pigment, or their composition and mixture. The above-mentioned organic pigments can also be used as crude pigments.

[Crystal size]

1. The first aspect of the present invention

In the first aspect of the present invention, the pigment particles of the present invention are characterized in that among the 8 planes (±1 ±1 ±1) of the crystal lattice plane calculated by X-ray diffraction pattern, it is combined with X-ray The crystallite size in the direction of the plane corresponding to the largest wave peak in the diffraction pattern (hereinafter referred to as "plane α") is less than 140 Å, and the compound represented by the aforementioned general formula (I) contains more than 90%.

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

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

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

2. The second aspect of the present invention

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

The size of the crystallites in the plane α direction 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 of the plane is preferably 80 Å or less, more preferably 75 Å or less, and even more preferably 70 Å or less. It is more preferable that the crystallite size in the plane α direction is 140Å or less and the crystallite size in the β direction is 80Å or less, and it is more preferable that the crystallite size in the plane α direction is 130Å or less and the crystallite size in the β direction is 75Å or less. , It is particularly preferable that the crystallite size in the α direction of the plane is 120 Å or less and the crystallite size in the β direction of the plane is 70 Å or less. It is best that the crystallite size in the plane α direction is 100Å or less and the crystallite size in the β direction is 70Å or less.

When the pigment type contains the compound represented by the above general formula (II), the plane α is the above-mentioned (1 1 1) plane, corresponding to 2θ=24.5°±0.3°, and the plane β is as shown in Fig. 6 (1 5 -1) plane, corresponding to 2θ=28.0°±0.3°. Therefore, when the pigment species contains the compound represented by the above general formula (II), the crystallite size of the lattice plane corresponding to 2θ=24.5°±0.3° is 140Å or less, and corresponds to 2θ=28.0°±0.3° The crystallite size of the lattice plane is preferably 80Å or less.

3. The third aspect of the present invention

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

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

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

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

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

Table 1 shows the relationship between the (02 0) plane, (1 1 1) plane, (1 5 -1) plane and the Bragg angle (2θ) of the 3 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 by having a crystallite size in the plane α direction of 140 Å or less and containing the compound represented by the aforementioned formula (III) (bromodiketopyrrolopyrrole).

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

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

3-1 crystallite size

Generally speaking, light is easily scattered at the interface between the crystallites constituting the primary particles and the crystallites (crystal grain boundaries), and it is known that the grain boundary is the main cause of light scattering. Therefore, in order to improve the optical properties of the pigment particles, it is considered to reduce the area of the crystal grain boundaries in the particles to reduce the influence of the crystal grain boundaries. Therefore, attempts have been made to reduce crystal grain boundaries in various fields. When reducing the area of the crystal grain boundary, the larger the crystallite size is better. However, after review by the inventors, it was unexpectedly discovered that the pigment particles of the present invention, which have smaller crystallite sizes as described above, have excellent optical properties. The mechanism by which the pigment fine particles of the present invention exerts more excellent optical properties due to the crystallite size of the pigment particles of the present invention is not fully clarified, but it is assumed to be as follows.

When the size of the crystallites is small, the The number of interfaces (crystal grain boundaries) increases, but the area of each crystal grain boundary decreases. It is generally considered that when the area of the crystal grain boundary is large, light is easily scattered. In contrast, the present invention speculates that by controlling the size of the crystallites to be small, the area of the crystal grain boundary becomes smaller, the light scattering is reduced, and the contrast and brightness of the resulting color filter are improved. Here, the small crystallite size means that the crystallite size in the α direction of the plane is 140 Å or less, and the crystallite size in the β direction of the plane is 80 Å or less.

Furthermore, as shown in FIG. 7, the primary particles of the pigment are composed of crystallites, so by reducing the size of the crystallites, the primary particles can also be made smaller. Because of the small primary particles and the high transmittance of the color filter, light scattering is suppressed, and contrast and brightness are improved. Here, the small primary particles of the pigment means that the average primary particle size is 40 nm or less.

In addition, when the diketopyrrolopyrrole-based pigment compound represented by the general formula (I) has anisotropic crystals, it is impossible to completely prevent birefringence caused by the crystal itself not due to grain boundaries. Especially in the case of a diketopyrrolopyrrole pigment compound (the above general formula (II)) having a substituent at the para position, it has a herringbone texture structure, and the space group is P21/n, which is relative to the para position Substituents or Tert-butyl-diketopyrrolopyrroles have a brick wall structure, and the space group is P1 (there is a bar (-) above P1), and the symmetry is low, And high anisotropy. Therefore, by setting the crystallite size of face α to 140 Å or less, and setting the crystallite size of face β to 80 Å or less, as described later, more improved isotropy and excellent optical properties can be obtained. As shown in the following number 1, a horizontal bar (-) is attached to P1.

In addition, the pigment microparticles of the present invention are small in primary particles, so it is possible to suppress undesirable conditions such as the occurrence of foreign matter caused by coarse primary particles.

When the crystallite size is large, the primary particles will inevitably become larger. As the size of the crystallites becomes larger, the primary particles also become larger, which hinders the contrast of the color filter and increases the brightness.

The crystallite size exceeds the upper limit of the scope of the present invention. For example, when the crystallite size in the α direction exceeds 140 Å and the crystallite size in the β direction exceeds 80 Å, the contrast and brightness of the resulting color filter are insufficient. In addition, foreign matter is likely to be generated due to coarse particles.

In addition, the lower limit of the crystallite size is not particularly limited, but if it is too small, the primary particles will become smaller than necessary, and the specific surface area of the primary particles will increase. As the specific surface area of the primary particles increases, the surface energy of the particles increases, and the dispersion of the pigment particles into the dispersion medium becomes difficult. Specifically, during dispersion, the pigment particles are aggregated, or the viscosity of the pigment dispersion in which the pigment particles are dispersed in the dispersion medium increases, or the possibility of increasing viscosity or gelation due to changes over time increases. In order to stabilize the dispersion, because the pigment dispersion contains many dispersants, the resulting color filter contains less colored components, and the characteristics of the color filter are increased due to unnecessary dispersant components, thus causing color characteristics There is a high possibility of the reduction of the color filter or the poor steps in the production of the color filter. In addition, it is technically difficult to make the crystallite size too small. On the contrary, the inventors found that it does not need to be so small to obtain sufficient The performance is improved. Therefore, it is only necessary to reduce the crystallite size to the above upper limit or less.

3-2 The ratio of crystallite size to average primary particle size

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

The above-mentioned crystallite size ratio, that is, the aspect ratio (hereinafter also referred to as "the aspect ratio of the crystallite size") is small, means that the crystallites are close to spherical. When it is close to a spherical shape, when the primary particles are formed, the crystallites are densely packed, and the crystallites in the primary particles are easily arranged in a manner with less anisotropy. By reducing the anisotropy in the primary particles, the primary particles become optically uniform, thus improving the contrast and brightness. In addition, since the crystallites are close to a spherical shape, the primary particles formed by the assembly of the crystallites also become spherical and have a small aspect ratio. Because the primary particles are nearly spherical, the pigment particles become difficult to align in the cured film of the pigment microparticles containing the aggregate of the primary particles, and the anisotropy of the cured film is reduced, thereby improving the contrast and brightness.

In addition, by setting the above-mentioned crystallite size ratio within the scope of the present invention, the pigment dispersion in which the pigment particles are dispersed in the dispersing medium can also reduce the amount of dispersant added, and achieve a low viscosity and good dispersibility. It may be that the length and width of the primary particles are relatively small, so it is speculated that the specific surface area of the pigment particles formed by the primary particles is small, and the pigment particles with a small particle surface energy can be obtained, and the aggregation of the particles is suppressed.

When the aspect ratio of the above-mentioned crystallite size exceeds the scope 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) that defines the ratio of the crystallite size to the crystallite size and the sum 2θ=3 calculated by the X-ray diffraction pattern The surface corresponding to the maximum peak of ~10° (surface γ), but these surfaces can be used as an index of isotropy. It is a revolutionary discovery that was reviewed by the inventors.

However, even if the aspect ratio of the crystallites is small, if the average primary particle size is large, the contrast and brightness of the resulting color filter will decrease. In addition, when the average primary particle size is 5 nm or less, even if the ratio of crystallite size is within the above range, the specific surface area of the primary particles becomes large and they tend to agglomerate, making it difficult to obtain a good dispersion. Therefore, only the ratio of the size of the crystallites is within the above range and the primary particle size is also within the above range. For example, in the case of pigment fine particles with an average primary particle size in the range of 5-40 nm, high contrast and high brightness can be obtained. Color filters.

[Measurement of crystallite size]

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

Among the diketopyrrolopyrrole pigments, the crystal structure of CIpigment red 254 is in the literature (Acta. Cryst. B49, 1056 (1993)). The X-ray crystal structure is analyzed and analyzed. The pigment is CIpigment red 254. When, use this to measure the crystallite size. Also, brominated diketopyrrolo The X-ray diffraction pattern of pyrrole is shown in Figure 4. Compared with 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 structure and the crystal lattice plane similar to CIpigment red 254 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 lattice plane described above is based on the following conditions and procedures.

(1) The powder X-ray diffraction measurement of the sample using CuKα line is performed within the range of Bragg angle (2θ) from 5.3° to 60°.

(2) From the X-ray diffraction pattern obtained in (1), find the diffraction pattern after removing the background. The method of removing the background is to use the Bragg angle (2θ) of the above-mentioned measurement pattern at around 5.3°, around 6.5°, around 10°, and around 60° to connect straight lines as the background, and find the X-ray winding obtained from (1) The operation of removing the pattern of the X-ray diffraction intensity value represented by the background from the intensity value

(3) The X-ray diffraction pattern obtained from (2) with the background removed, in the compound represented by general formula (II), the Bragg angle (2θ) of the diffraction peak characteristic of the (0 2 0) plane, respectively = 7.4°±0.3° near the diffraction peak and (1 1 1) surface characteristic diffraction peak Bragg angle (2θ) = 24.5°±0.3° near the diffraction peak, (1 5 -1) surface The Bragg angle (2θ) of the characteristic diffraction peak = the diffraction peak near 28.0°±0.3°, find the half width and the Bragg angle (2θ) of the diffraction peak. The half-width is calculated by using commercially available data for each of the 3 diffraction peaks existing in the above measurement range Analyze the software, and the peak separation can be calculated. For example, in the following embodiment, the data analysis software HighScorePlus Ver.3.0e (3.0.5) manufactured by PANalytical is used, and the peak shape is used as the Pseudo Voigt function, and fitting is performed using the calculated half-width value.

(4) Calculate the crystallite size by using the half-height width of the diffraction peak calculated in (3) and the following Scherrer formula.

D=Kλ/(B×cosA)

B=Bobs-b

here,

D: Crystallite size (Å)

Bobs: half-height (rad) calculated by (3)

b: X-ray diffraction device angle resolution correction coefficient, the half-maximum width (rad) of standard silicon crystal measurement. The standard silicon crystal was measured with the following device configuration and measurement conditions, b=0.087.

A: Bragg angle of diffraction peak 2θ(rad)

K: Scherrer constant (defined as K=0.90)

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

The measurement conditions are detailed as follows.

X-ray diffraction device: Multi-purpose X-ray diffraction device X’Pert P manufactured by PANalytical

owder goniometer: high-precision sample horizontal goniometer manufactured by PANalytical

Sampling width: 0.0131°

Step time: 0.335 seconds

Divergence slit: program divergence slit

Incident side scattering slit: none

Soller slits on the incident side: 0.04°

Incident side mask: 10mm

Scattering slit on the receiving side: 8mm

Parallel plate slit on the light receiving side: 0.04°

Tube ball: Cu

Tube voltage: 45kV

Tube current: 40mA

In addition, as long as it is a method that can obtain the same result as the above method, other methods may be adopted.

[Calculation of crystallite size ratio]

The crystallite size of each plane obtained by the foregoing method is calculated by dividing the crystallite size of the (1 1 1) plane by the crystallite size of the (0 2 0) plane to calculate the difference between the (1 1 1) plane and the (0 2 0) plane. 2 0) The ratio of the crystallite size of the plane.

[Change rate of interplanar spacing between lattice planes]

The diketopyrrolopyrrole pigment particles of the present invention are calculated by X-ray diffraction pattern before and after heating, and the value of the interplanar spacing of the lattice plane corresponding to the maximum peak of 2θ=3~10° 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. It is more preferably 2.0% or less, particularly preferably 1.5% or less.

The rate of change between the value under 80℃ and the value under 230℃={(under 230℃ Surface interval)/(surface interval at 80℃)×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. The (0 2 0) plane is a plane roughly perpendicular to the long axis of the crystal lattice. Compared with other lattice planes, the rate of change of the interplanar spacing due to heating is the largest, so it can be an indicator of the stability of the crystal structure described later. .

Other diketopyrrolopyrrole pigments are also the same as CIpigment red 254 or brominated diketopyrrolopyrrole. The surface corresponding to the largest wave peak in 2θ=3~10° becomes the surface approximately perpendicular to the long axis of the crystal lattice. Compared with other crystal lattice planes, the rate of change of the interplanar spacing caused by heating is the largest, so it can be an indicator of the stability of the crystal structure.

When the color filter is manufactured, there is a step in which the pigment is heated, and the color characteristics will deteriorate due to the amount of heating. Specifically, it becomes a problem of hue shift, contrast, and brightness reduction due to heating. In this regard, the pigment fine particles of the present invention can suppress the deterioration of the color characteristics due to heating by setting the change rate of the interplanar spacing to 3.0% or less, and can obtain a higher-quality color filter.

In the present invention, by using pigment particles with a small change rate of the interplanar spacing between the lattice planes, it is possible to obtain a color filter mechanism with more excellent optical characteristics. In addition, by using pigment particles with a smaller crystallite size or a smaller crystallite size Although the mechanism by which pigment particles with relatively small length and width can reduce the rate of change of the interplanar spacing between the lattice planes is not clear, it is presumed to be as follows.

The lattice plane spacing changes due to heating. In most cases, it changes in the direction in which the interplanar spacing expands. When the surface spacing is extended, the gap between the crystallites The area of the crystal grain boundary becomes larger, and as described above, it becomes a primary particle that easily scatters light, and it is estimated that the pigment fine particles are likely to cause a decrease in contrast or brightness. In addition, it is estimated that a large rate of change of the interplanar spacing due to heating indicates that the crystal structure is unstable, and the crystal structure changes due to heating, and the hue shift occurs due to the interaction of the electron orbits of adjacent molecules.

It is generally believed that the reason for the increase in the rate of change of the interplanar spacing due to heating is that many unstable elements are contained in the crystal structure. The unstable elements of the crystal structure include, for example, impurities, amorphous components, and strain of the crystal structure. There are various sizes of crystallites, or when the length and width of the crystallites are relatively large, there is strain in the crystal structure, or the adjacent parts of the crystallites contain many unstable amorphous structures. It is estimated that the crystal structure changes due to heating. The interaction of the electron orbitals of adjacent molecules produces a hue shift. In addition, it is considered that the unstable amorphous structure is crystallized by heating to generate foreign matter. In this regard, the pigment particles of the present invention are close to spherical due to small crystallites, so it is estimated that the strain of the crystal structure is small, compact and stable, and the change of the crystal structure due to heating is suppressed, and the rate of change of the interplanar spacing becomes small.

As long as the pigment particles of the present invention have a specific crystallite size or a specific crystallite size ratio, the crystal grain boundary that is the cause of the instability of the crystal structure can be suppressed, and the crystallites are densely assembled and stable. Crystal structure. Therefore, the change rate of the surface spacing due to heating can be controlled within the above range, for example, within 3.0%. That is, a pigment with a small interplanar spacing change rate due to heating and a stable crystal structure.

In addition, the method of measuring the rate of change of the interplanar spacing of the lattice plane by heating is performed as follows.

(1) Same as the aforementioned [Measurement of crystallite size], within the Bragg angle (2θ) of 5.3° to 50°, the powder X-ray diffraction measurement is performed by heating using CuKα line. Specifically, first, the X-ray diffraction pattern is measured at 25°C, and then the temperature is raised to 80°C, and after the temperature is maintained for 10 minutes, the X-ray diffraction pattern at 80°C is measured. In addition, 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), find the diffraction pattern after removing the background. The method of removing the background is to set the Bragg angle (2θ) of the above-mentioned measurement pattern = around 5.3°, around 6.5°, around 10°, and around 37.5°, respectively, using a straight line connection as the background, and find the X-ray winding obtained from (1) The operation of removing the value of the X-ray diffraction intensity from the pattern of the X-ray diffraction intensity indicated by this background.

(3) The X-ray diffraction pattern with the background removed from (2) is fitted using the data analysis software HighScorePlus Ver.3.0e (3.0.5) manufactured by PANalytical, and the peak shape is used as a Pseudo Voigt function. ), using the Bragg angle formula to calculate the Bragg angle (2θ) of the characteristic diffraction peak of the (0 2 0) plane = 7.4°±0.3° and the surface interval of the diffraction peak around.

2dsinA=nλ

here,

d: surface interval (Å)

A: Bragg angle of diffraction peak 2θ(rad)

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

n: integer

(4) Using the result of (0 2 0) plane spacing at 80°C and 230°C obtained in (3), the rate of change of the plane spacing caused by these temperature changes is calculated by the following specific formula.

The rate of change between the value at 80℃ and the value at 230℃={(plane interval at 230℃)/(plane interval at 80℃)×100}-100(%)[Specific formula]

The details of the measurement conditions are the same as the aforementioned [Measurement of Crystallite Size].

In addition, as long as it is a method that can obtain the same result as the above method, other methods may be adopted.

[Primary particle size]

The primary particle diameter of the diketopyrrolopyrrole pigment microparticles in the third aspect of the present invention is 5-40 nm. In addition, in the diketopyrrolopyrrole-based pigment particles in the first, second, and fourth aspects of the present invention, the primary particle size is preferably 5-40 nm. In any case, the primary particle size is preferably 10-30 nm, particularly preferably 15-25 nm. In addition, it is preferable that the standard deviation of the primary particle size is less than 7.0, more preferably less than 6.0, and particularly preferably less than 4.0. In addition, the coefficient of variation of the primary particle size (CV value: hereinafter referred to as "CV value") is preferably less than 30, more preferably less than 28, and particularly preferably less than 25.

By setting the primary particle diameter of the diketopyrrolopyrrole-based pigment fine particles to be equal to or less than the above upper limit, a high-contrast pigment dispersion can be obtained. In addition, by setting the primary particle size of the diketopyrrolopyrrole-based pigment particles at least the above lower limit, the viscosity at the time of preparing the dispersion can be reduced. It can also suppress the change in viscosity over time.

In the case of diketopyrrolopyrrole pigment fine particles having a primary particle size exceeding the above upper limit, the contrast may be lowered, and the performance required for use as a color filter may not be satisfied. In the case of diketopyrrolopyrrole pigment particles with a primary particle size that is less than the above lower limit, it becomes difficult for the pigment particles to disperse the dispersion medium. During the dispersion process, the dispersant or binder for the pigment dispersion The addition amount of compounds such as resins and pigment derivatives has become very large, so the application of the pigment dispersion to color filters will inevitably become difficult.

By setting the standard deviation of the primary particle diameter of the diketopyrrolopyrrole-based pigment particles below the above upper limit value, a pigment dispersion having particularly high contrast, low viscosity, and small change in viscosity over time can be obtained. When the standard deviation of the above-mentioned primary particle size exceeds the above-mentioned upper limit, since most of the primary particles of inconsistent size or shape exist, it is easy to cause the contrast of the pigment dispersion to decrease.

By setting the CV value of the primary particle diameter of the diketopyrrolopyrrole-based pigment particles below the above upper limit, it is possible to obtain a pigment dispersion having particularly high contrast, low viscosity, and small viscosity change over time. When the CV value of the above-mentioned primary particle size exceeds the above-mentioned upper limit, since most of the primary particles of inconsistent size or shape are present, it is easy to cause the contrast of the pigment dispersion to decrease.

Here, the primary particle size is a particle size calculated from an image obtained by observation with an electron microscope. The measurement methods of the primary particle size and its standard deviation and CV value are as follows.

Use 10 parts by weight of the pigment particles of the present invention as a dispersant "BYKLPN 6919" (manufactured by BYK-Chemie) has a solid content of 5 parts by weight, 1 part by weight of the sulfonated derivative of CIpigment red 254 as a dispersion aid, and propylene glycol monomethyl ether as an organic solvent as a dispersion medium 70 parts by weight of acetate was stirred and mixed with a paint mixer (manufactured by Asada Iron Works Co., Ltd.) for 6 hours of dispersion treatment to obtain a pigment dispersion. This pigment dispersion was diluted 50 times to 200 times with propylene glycol monomethyl ether acetate, and the diluted solution was treated with an ultrasonic homogenizer (manufactured by SND Co., Ltd., ultrasonic cleaner US-105) for 5 minutes After that, observe the particle image. This observation system uses S-5200 electric field release scanning electron microscope (produced by Hitachi High-Tech Co., Ltd.) with an acceleration voltage of 20kV and observation magnification of 1 million times. For 100 particles that can be clearly identified from the observation image, use SEM uses image analysis software (Scandium manufactured by OLYMPUS) to measure the long diameter and calculate the primary particle size and its standard deviation and CV value.

[Content of diketopyrrolopyrrole compound]

The pigment microparticles of the first aspect of the present invention contain more than 90% of the compound represented by general formula (I). In this way, by containing the compound represented by general formula (I) at a high concentration, the coloring power or brightness can be maintained at a high level. In order to reduce the crystallization of pigment fine particles, for example, it is possible to add a component that inhibits particle growth (for example, the pigment derivative described in Patent Document 5). However, when such a component is added, it becomes difficult to maintain high coloring power or brightness. In this regard, the pigment microparticles of the first aspect of the present invention are formed by containing the compound itself represented by general formula (I) in addition to the pigment derivatives and other components. The amount is maintained at a high content of more than 90%, and the coloring power or brightness can be maintained at a high level.

In addition, when the pigment particles of the second and third aspects of the present invention maintain high coloring power or brightness, the content of the compound represented by general formula (I) may be 90% or more, and is preferably. In the pigment microparticles 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 preferably.

The content of the diketopyrrolopyrrole pigment compound represented by general formula (I), general formula (II), and formula (III) can be limited as follows. Regarding the solvent extract of the pigment particles of the present invention, LC-MS analysis or NMR analysis is performed to identify the contained components and then quantitatively analyze. More specifically, the pigment fine particles are dissolved in an organic solvent such as tetrahydrofuran (hereinafter referred to as "THF"), and separated by LC-MS liquid chromatography for molecular weight analysis. In addition, the insoluble matter was directly introduced into the probe as a solid, and molecular weight analysis was performed. These are methods of identifying each component based on the molecular weight information of the whole and part of the molecule. In addition, the diketopyrrolopyrrole pigment compound represented by the general formula (I), general formula (II), and formula (III) of the components of the pigment particles can be compared with the standard substance of the identified components for quantitative analysis. In addition, the pigment particles are dissolved in heavy dimethyl sulfide or heavy sulfuric acid, and each component is identified by NMR measurement, and it can be quantified by the area ratio of the NMR spectrum.

[Performance of the pigment particles of the present invention]

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

Here, the contrast is one of the indicators of the color characteristics of the pigment. The higher contrast is used in optical materials such as displays, and the color development is colorful, so it is better. The measurement of comparison is to use a contrast measurement device to irradiate light on a cured film sandwiched between two polarizing plates, and the amount of light transmitted when the polarizing surfaces of the front polarizing plate and the rear polarizing plate are parallel and at right angles, using a comparative measuring device ( CT-1 manufactured by Kosaka Electric Co., Ltd.). The transmitted light is used as the brightness of the polarizer. The ratio of the brightness when the polarizing plane of the polarizer is parallel to the brightness when it is at a right angle is measured by contrast ((contrast)=(polarizing surface of the polarizer) Is the brightness when parallel)/(the brightness when the polarizing plane of the polarizer is at right angles)) calculation.

In addition, when the film thickness of the cured film has 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 with high coloring power can be obtained, which is preferable. The thickness of the film is to use a non-contact surface. The layer profile shape measurement system (R5300G-Lite manufactured by Ryoka System Co., Ltd.) performs measurement.

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

In addition, when observing the cured film with an optical microscope at a magnification of 500, the number of confirmed coarse particles can be suppressed to 50 or less, and further to 20 or less.

In addition, brightness is one of the indicators that contrast the color characteristics of the same pigment. Those with higher contrast and brightness values are better when used in optical materials such as displays, which have rich colors and can suppress the amount of light in the backlight. The measurement of brightness is obtained by measuring the cured film using a spectrophotometer (LCF-1100 manufactured by Otsuka Electronics Co., Ltd.).

With the pigment particles of the present invention having a specific crystallite size or a specific crystallite size ratio, the mechanism for providing a color filter with extremely excellent optical characteristics as described above is not clear, but as mentioned above, it is speculated that The size of the crystallites, such as the size of the crystallites in the α direction of the plane, should be controlled below 140 Å, and the size of the crystallites in the β direction of the plane should be controlled below 80 Å, or the crystallite size ratio should be controlled within the range of, for example, 0.85 to 1.25. It can suppress the occurrence of crystalline strain, and contribute to the stability of the structure, with little change when heated (the performance is improved by reducing the change caused by heating). In addition, it is presumed that it contributes to the suppression of light scattering that affects the crystal interface (the optical influence of the crystal grain boundary). In addition, it is speculated that by setting the ratio of the size of the crystallites to the size of the crystallites to reduce the size and shape of the primary particles, and form isotropy, it is helpful to make the primary particles exist in a good state in the cured film (primary The influence of the state of the particles in the cured film). It is inferred that the multiplying effect of these plural elements will achieve the excellent effect of the invention, which is difficult to achieve by the prior art after all.

In addition, in a cured film such as a color filter or in a photosensitive coloring composition, the general formula (I), the general formula (II), and the formula (III) are expressed The content of the diketopyrrolopyrrole pigment compound can be limited as follows. Regarding the solvent extract of the cured film or photosensitive coloring composition, LC-MS analysis or NMR analysis is performed to identify the contained components and then quantitatively analyze. More specifically, the cured film or the photosensitive coloring composition is dissolved in an organic solvent such as THF, and separated by LC-MS liquid chromatography for molecular weight analysis. In addition, the insoluble matter was directly introduced into the probe as a solid, and molecular weight analysis was performed. In addition, the diketopyrrolopyrrole pigment compound represented by general formula (I), general formula (II), and formula (III) among the components of the cured film or photosensitive coloring composition can be compared with the standard substance of the identified component Perform quantitative analysis. In addition, the cured film or photosensitive coloring composition is dissolved in heavy dimethyl sulfide or heavy sulfuric acid, and each component is identified by NMR measurement, and it can be quantified from the area ratio of the NMR spectrum.

[Production method]

The method for producing diketopyrrolopyrrole pigment particles of the present invention is not particularly limited, and the so-called salt milling method, the so-called reprecipitation method, or a combination of the salt milling method and the reprecipitation method can be used to refine the organic pigment. The aforementioned various conventional technologies are manufactured.

Among them, it is easier to control the crystallite size or primary particle size, and it is better to use the reprecipitation method, which has less risk of causing pigment crystal strain due to excessive energy input, such as the salt milling method. In the reprecipitation method, a solution in which organic pigments are dissolved in a good solvent (hereinafter also referred to as "pigment dissolving liquid") and a weak solvent of organic pigments that are compatible with the good solvent (hereinafter also referred to as "weak solvent") are continuous Supply the reaction field and mix the two to make the precipitated pigment particles It is better to take it out from the liquid and continuously carry out the pigment precipitation reaction by a continuous reaction device.

Especially the mixed use of pigment solution and weak solvent can be close. The separation and relative rotation processing is most suitable for mixing with a reaction device (hereinafter also referred to as a "fluid processing device") in a continuous process between surfaces. The reaction device is formed in close proximity. The separation state is relative to the rotation of the processing surface, and the special environment of the thin film fluid forced by the processing surface, the mixing of the pigment solution and the weak solvent and the precipitation of the pigment particles are compared with the previous microreactor or other Mixing and stirring device, there are obvious distinctions. In addition, the pigment solution and the weak solvent are close to each other. The separated state is mixed with the small space between the rotating processing surfaces, which can essentially eliminate the influence of gravity. In addition, the precipitation of the pigment particles using this reaction device is preferably carried out under laminar flow conditions rather than turbulent flow conditions. .

The reason why this method is better is as follows.

First, in the case of mechanically pulverizing the pigment by a salt grinding method, the crystallite size is pulverized to, for example, the crystallite size in the α direction of the plane is 140 Å or less, and the crystallite size in the β direction of the plane is 80 Å or less. Very large force. In addition, crystal growth occurs at the same time as pulverization, so the production reaction must be in a balanced state, which is difficult to control and poor in productivity. In the case of the reprecipitation method, once the pigment is dissolved, it is easier to control the particle size. However, in the case of the reprecipitation method, it is not easy to control the crystallite size. As the reaction continues, the crystallites gradually grow, so this phenomenon must be prevented. Therefore, it is considered that the contact between the pigment solution in the reaction field and the weak solvent proceeds quickly, so that a large number of small crystallite size particles are generated. Therefore, the diffusion coefficient of the reaction field changes It's important. Therefore, it is considered that a continuous reaction device that continuously recovers the generated pigment particles by continuously supplying the pigment solution and the weak solvent to the reaction field is preferable. Especially the mixture of pigment solution and weak solvent can be used in close proximity. When the separation and relative rotation process uses a continuous surface-to-surface reaction device, the diffusion coefficient of the reaction field becomes larger, and a large number of crystal nuclei are generated, so that fine and crystallite pigment particles can be efficiently obtained.

Reprecipitation method, especially in the approachable. The separation and relative rotation process uses the method of continuous precipitation reaction of the pigment particles between the surfaces, and the resulting pigment particles are very fine, and the particles are uniformly produced, and the crystallite size and distribution are small. That is, the resulting pigment particles are extremely fine pigment particles with a small number of coarse particles and uniform particle diameters, and the occurrence of crystal strain and the like are suppressed. It is presumed that this is because the contact between the pigment solution and the weak solvent is carried out at extremely high speed, so the diffusion coefficient of the reaction field becomes larger, and a large amount of fine crystal nuclei can be purified, and the pigment of the aggregate of fine crystallites can be obtained. Fine particles, and the excessive energy provided by grinding treatment such as salt grinding treatment is not input, and the generation of strain can be suppressed.

The pigment fine particles obtained by the above method are in good condition such as crystals, and there are few coarse particles that hinder colorability, so that a pigment fine particle dispersion having excellent heat resistance and coloring properties can be obtained. In other words, not only the primary particle size of the pigment particles, but also by controlling the size or distribution of the crystallites, a color filter with improved color characteristics, heat resistance, and other characteristics and 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 "the pigment precursor") is dissolved in a good solvent. The original pigment system refers to the pigment before the micronization process described below. The diketopyrrolopyrrole-based pigment precursor is not particularly limited, and well-known commercially available pigments can be used, and pigments produced by methods disclosed in various prior art related to the manufacturing method of the aforementioned diketopyrrolopyrrole-based pigments can also be used.

Good solvents for dissolving the diketopyrrolopyrrole pigment precursor include, for example, water, organic solvents, or mixed solvents composed of a plurality of them. The above-mentioned water includes tap water or ion exchange water, pure water or ultrapure water, RO water, etc. The organic solvent includes alcohol-based solvents, amide-based solvents, ketone-based solvents, ether-based solvents, aromatic solvents, carbon disulfide, and fats. Group solvents, nitrile solvents, sulfite solvents, halogen solvents, ester solvents, ionic liquids, carboxylic acid compounds, sulfonic acid compounds, etc. The above-mentioned solvents may be used singly, or a plurality of them may be mixed and used.

Here, inorganic hydroxides such as sodium hydroxide or potassium hydroxide, or metal alkoxides such as sodium methoxide or potassium tert-butoxide, or quaternary ammonium compounds can be present in the above-mentioned good solvent. Known. In the present invention, it is particularly preferable to add the quaternary ammonium compound to the above-mentioned good solvent. By adding a quaternary ammonium compound to the above-mentioned good solvent, it is particularly easy to control the characteristics of the present invention to a specific crystallite size and primary particle size. Although the mechanism is not clear, the presence of the quaternary ammonium compound in the solvent brings good results for the dissolution of the diketopyrrolopyrrole compound pigment precursor and subsequent precipitation, especially for improving the color characteristics. result.

A quaternary ammonium compound that can be added, benzyl trimethyl can be used Hydroxides, chlorides, bromides such as ammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrahexylammonium, etc., but among them, from the viewpoint of improving solubility, preferred are The hydroxide is particularly preferably benzyltrimethylammonium hydroxide or tetramethylammonium hydroxide. These can be used alone or in combination of two or more kinds.

In addition to these, tetradecyldimethylbenzylammonium chloride, tetra-N-butylammonium tribromide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, etc. may also be used.

The addition amount of the quaternary ammonium compound is relative to the original pigment, preferably 0.1-10 molar equivalent. In addition, relative to the original pigment, it is more preferably 0.3-6 molar equivalent, particularly preferably 0.5~ 4 molar equivalent. By adding more than 0.1 molar equivalent to the original pigment, the original pigment can be fully dissolved, which is beneficial to the precipitation step of the pigment fine particles and can suppress the occurrence of coarse particles. In addition, by suppressing it to 10 molar equivalents or less relative to the original pigment, the amount of the original pigment in the solvent can be optimized and good productivity is obtained. Therefore, it is preferable to suppress the accelerated decomposition of the molecules of the original pigment. It can provide better effects on heat resistance and color characteristics, so it is better.

The preparation method of the pigment dissolving liquid is not particularly limited, but it is better to prepare it using a mixer having a rotating stirring blade. By this, of course, it is possible to suppress the dissolution of two or more molecules or elements due to the undissolved matter in the pigment dissolving liquid from generating coarse particles, and it is also possible to quickly produce a pigment dissolving liquid in a more uniform dissolved state.

Presumably by using a mixer with rotating mixing blades By preparing the pigment dissolving liquid, it is possible to obtain a pigment dissolving liquid in a uniform dissolution state or a molecular dispersion state at the molecular level, which can improve the dissolution state of the pigment dissolving liquid or forming a fine particle (cluster) state.

The stirrer used for the preparation of the pigment solution is not particularly limited as long as it has a rotating stirring blade. A general stirrer with a rotating stirring blade. The peripheral speed of the tip of the stirring blade is 1m/sec or more, which is called high-speed rotation. . It can also be implemented at a low speed of less than 1 m/sec. However, from the viewpoint of shortening the time for dissolving the pigment or improving the reliability of the dissolution of the pigment, a high-speed rotating mixer is preferred. From the viewpoint of suppressing the generation of coarse particles, the pigment dissolving liquid is prepared at a peripheral speed of 1 m/s or more, preferably 10 m/s or more. Such a mixer is preferably various dispersers, for example, a high-speed rotary emulsifying disperser (manufactured by m-technique Co., Ltd., product name: CLEARMIX).

For the concentration of the diketopyrrolopyrrole-based pigment precursor in the pigment solution, from the viewpoint of productivity, the higher concentration is better. Preferably it contains 3 weight% or more, More preferably, it contains 5 weight% or more.

The pigment dissolving liquid is mixed with the weak solvent to precipitate pigment fine particles. The solvent used for the weak solvent can be selected from the solvents listed as good solvents for dissolving the diketopyrrolopyrrole pigment precursor, but a solvent with low solubility for the organic pigment contained in the pigment solution must be selected. Each of these solvents can be used alone or in a mixture of more than one. In addition, in order to adjust pH, particle size, and degree of crystallinity, an acid may be added. When the added acid is an organic acid, carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, benzenesulfonic acid, cyclohexanesulfonic acid, p-toluenesulfonic acid, etc. can be used. Phenols such as sulfonic acid, salicylic acid, cresol, thymol, etc. In addition, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, hexafluorophosphoric acid, aminosulfonic acid, and perchloric acid may also be used. Each of these can be used singly or in a mixture of more than one. The addition of acid may sometimes bring about a situation where the color characteristics are further improved. In addition, in the step of preparing the weak solvent, as in the preparation of the pigment dissolving liquid, it is preferable to use the aforementioned agitator having a rotating stirring blade.

The pigment dissolving liquid and the weak solvent are mixed to precipitate the pigment fine particles. As mentioned above, the mixture of the two is close. It is better to use continuous mixing between surfaces for the processing of separation and relative rotation.

The temperature at which the pigment particles precipitate 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 so that the temperature during precipitation becomes 50°C or less, finer particles can be precipitated. It is particularly preferable that the temperature during precipitation is 30°C or less. It is estimated that the precipitation of pigment fine particles at a high temperature exceeding 50°C promotes the crystal growth of the pigment fine particles and the precipitation of coarse particles. When the pigment fine particles are precipitated at a temperature below 50°C, the crystal growth of the fine particles is suppressed and the crystallite size is If it is smaller, the pigment particles with a fine and uniform primary particle size will be precipitated.

By mixing the pigment solution and the weak solvent, the pigment particles are precipitated, and the resulting slurry containing the pigment particles is filtered, centrifuged, dialysis, critical filtration and other methods are used to remove the pigment particles from the liquid and use various solvents. After washing, the pigment particles of the present invention can be separated. The solvent used for washing can be selected as a dissolving diketopyrrolo Solvents listed as good solvents for pyrrole-based pigment precursors. In addition, in the washing treatment, it is preferable to use the aforementioned agitator having a rotating stirring blade. The end point of the cleaning is not particularly limited, and it can be determined by the pH of the cleaning solution, the analysis of impurity ions or organic matter. In addition, the cleaned pigment particles contain the solvent used in the cleansing at the end of the cleansing, so they must be dried or replaced by the solvent.

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

The method of solvent substitution is not particularly limited. After the cleaning, the resulting wet cake containing the pigment particles of the cleaning solution is put into the target solvent, and the solution is uniformized by stirring, and then filtration and centrifugation are used again. Separation, dialysis, critical filtration, etc. can be used to make a wet cake of pigment particles containing solvents.

The precipitation of the pigment particles by the reprecipitation method and the cleaning treatment of the precipitated pigment particles can be said to be not only the precipitation of the pigment particles, but also the treatment that accompanies the purification of the original pigment. It is speculated that by dissolving the original pigment into a molecular state, impurities such as metals or unreacted substances contained in the pigment particles are extracted, and these impurities are removed by washing the pigment particles after precipitation. The inventors of the present invention believe that one of the reasons for the superior coloring power of the pigment particles by the reprecipitation method compared to the salt milling method represented by Patent Documents 1 and 2 is the purification of the pigment precursor. .

Use this pigment when the amount of Fe contained in the pigment particles is large When a color filter is made with fine particles, the liquid crystal may malfunction due to a decrease in the voltage holding ratio. In addition, the large amount of Fe contained in the pigment particles not only increases the amount of impurities contained in the color filter, but also reduces the color characteristics or tinting power. In addition, it may be caused during the baking step during the production of the color filter described later. The cause of foreign matter on the coating film. Therefore, it is necessary to reduce the amount of Fe contained in the pigment particles as much as possible. According to the purification effect of the original pigment by the reprecipitation method described above, it is known that the amount of Fe can be reduced. Therefore, the Fe content in the pigment particles can be reduced to 35 ppm or less. More preferably, it is reduced to 30 ppm or less, and even more preferably, it is reduced to 20 ppm or less.

[An example of manufacturing equipment]

Here, for those with the above can be approached. The fluid processing device of the separated and relatively rotating processing surface is briefly described with reference to Figs. 1 to 3. This device is the same as that described in Patent Document 7.

In FIG. 1, U represents the upper side, and S represents the lower side. However, in the present invention, the up, down, front, back, left, and right are only relative positional relationships, and they are not limited to absolute positions. In Fig. 2(A) and Fig. 3(B), R represents the direction of rotation. In Fig. 3(B), C represents the direction of centrifugal force (radial direction).

This fluid processing apparatus is provided with two opposing first and second processing parts 10 and 20, and at least one of the processing parts rotates. The opposing surfaces of the two processing parts 10 and 20 respectively serve as processing surfaces. The first processing member 10 includes a first processing surface 1, and the second processing member 20 includes a second processing surface 2.

The two processing surfaces 1, 2 and the fluid (that is, the above-mentioned pigment soluble The solution is connected to the flow path of the above-mentioned weak solvent, and constitutes a part of the flow path of the fluid to be processed. The interval between the two processing surfaces 1 and 2 can be appropriately changed and implemented, 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 thin film fluid forced by the two processing surfaces 1 and 2.

When using this device to process a plurality of fluids, the device is connected to the flow path of the first fluid to form a part of the flow path of the first fluid. In addition, this device forms a part of the flow path of the second fluid that is different from the first fluid. In this device, 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 to precipitate fine particles.

When specifically described, this device includes: a first fixed bracket 11 that holds the first processing member 10, a second fixed bracket 21 that holds the second processing member 20, a contact pressure applying mechanism, a rotation drive mechanism, 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 a ring-shaped body, and more specifically, it is a ring-shaped disk. In addition, the second processing member 20 is also an annular disk. In this embodiment, the first and second processing surfaces 1 and 2 of the two processing parts 10 and 20 facing each other are mirror polished, and the arithmetic average 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, to The lesser fixed bracket can be a rotation drive mechanism (not shown) such as a motor, and the other fixed bracket can be relatively rotated.

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

In this embodiment, with respect to the first processing member 10, the second processing member 20 can approach the direction of the rotation axis 50. When separated, the portion on the opposite side to the processing surface 2 side of the second processing portion 20 can be stored in and out of the housing portion 41 provided in the second fixing bracket 21. However, on the contrary, the first processing member 10 may be close to and separated from the second processing member 20, or the two processing members 10 and 20 may be close to each other and separated.

This accommodating part 41 is a recessed part accommodating the part on the side opposite to the processing surface 2 side of the 2nd processing member 20, and forms an annular groove. This accommodating portion 41 has a sufficient gap to allow the portion on the side opposite to the processing surface 2 side of the second processing portion 20 to flicker and flicker, and to accommodate the second processing portion 20. The second processing member 20 can be arranged to move only in parallel in the axial direction, but by increasing the above gap, the second processing member 20 can tilt and shift the center line of the processing member 20 with respect to the accommodating portion 41 , Break the parallel relationship with the axial direction of the accommodating portion 41. In addition, the center line of the second processing member 20 and the center line of the accommodating portion 41 may be offset in the radial direction. Separation, displacement. In this way, it is preferable to hold the second processing member 20 by holding a floating mechanism capable of three-dimensional displacement.

The above-mentioned flow system is introduced between the two processing surfaces 1 and 2 from the first introduction portion d1 and the second introduction portion d2 in a state where pressure is applied by a fluid pressure applying mechanism p composed of a pump or positional energy. In this embodiment, the first introduction portion d1 is a passage provided in the center of the ring-shaped second fixed bracket 21, and one end is introduced into the two processing surfaces 1 from the inner side of the two ring-shaped processing portions 10 and 20. , 2 rooms. The second introduction part d2 supplies the second fluid that reacts with the first fluid to the processing surfaces 1 and 2. In this embodiment, the second introduction portion d2 is a passage provided inside the second processing member 20, and one end of the passage is formed in the opening d20 of the second processing surface 2.

The first fluid pressurized by the fluid pressure applying mechanism p is introduced into the space inside the two 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 In between, it passes through to the outside of the two processing parts 10 and 20.

Between these 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, by the above-mentioned pigment dissolving liquid when the two fluids are mixed The precipitation reaction with the aforementioned weak solvent precipitates organic pigment particles, and the fluid containing the organic pigment particles is discharged from the two processing surfaces 1 and 2 to the outside of the two processing parts 10 and 20.

The aforementioned contact pressure imparting mechanism imparts a force acting in a direction approaching the first processing surface 1 and the second processing surface 2 to the processing portion. In this embodiment, the contact pressure imparting mechanism is provided on the second fixed support The frame 21 energizes the second processing member 20 to the first processing member 10.

The above-mentioned contact pressure applying mechanism is used to generate a force in the 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 approach (hereinafter referred to as the contact surface). Pressure). By balancing the contact pressure and the force separating the two processing surfaces 1 and 2 with fluid pressure, the space between the two processing surfaces 1 and 2 is kept at a specific minute interval, resulting in a unit with nm to μm Thin film fluid with a unit of tiny film thickness. In addition to the elastic force of the spring 43, the pressure of the energizing fluid such as air or oil introduced into the energizing fluid inlet 44, the contact pressure may also be other forces such as magnetic force or gravity.

Resisting the energization of the contact pressure applying mechanism, the separation force generated by the pressure and viscosity of the fluid pressurized by the fluid pressure applying mechanism p makes the second processing member 20 away from the first processing member 10, A small gap is opened between the processing surfaces. In this way, by the balance between the contact pressure and the separating force, the interval between the first processing surface 1 and the second processing surface 2 is set with an accuracy of μm.

The above-mentioned separation force includes, in addition to the fluid pressure or viscosity of the fluid, the centrifugal force formed by the rotation of the processing part, the negative pressure when the negative pressure is applied to the energizing fluid introduction part 44, and the extension of the spring 43. The elasticity of time and so on. This contact pressure applying mechanism is not provided in the second processing section 20, but may be provided in the first processing section 10, or may be provided in both.

As shown in FIG. 2, the first processing surface 1 of the first processing member 10 may be formed from the center side of the first processing member 10 to the outside, That is, it is implemented by a groove-shaped recess 13 extending in the radial direction. As shown in FIG. 2(B), the planar shape of the recess 13 may be a curved or spiral shape extending from the first processing surface 1. In addition, this recessed part 13 may be formed in the 2nd processing surface 2 and can be implemented, and it can also be implemented in the 1st and 2nd processing surface 1 and 2 both. By forming such a concave portion 13, a micro-pumping effect can be obtained, and there is an effect of sucking 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 this recessed portion 13 extends to the outer peripheral surface side of the first processing portion surface 1, and the depth thereof gradually decreases from the base end to the front end.

A flat surface 16 without the recess 13 is provided between the front end of the recess 13 and the outer peripheral surface of the first processing surface 1.

The aforementioned opening d20 is preferably provided at a position facing the flat surface 16 of the first processing surface 1.

Especially set in the flow direction when introduced by the micro-pumping effect, and compared to the spiral formed between the processing surfaces, the point at which the flow direction is converted into laminar flow is further downstream (in this case, the outside) The position opposite to the flat surface 16 is preferable.

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

The shape of the opening d20, as shown in Figure 2 (B) or Figure 3 (B), can be a circular shape, as shown by the dotted line in Figure 2 (B), or it can be wound The processing surface of the ring-shaped disc is in the shape of a concentric circular ring with the central opening of the surface 2.

In order to easily obtain the pigment fine particles with controlled crystallite size and primary particle size of the present invention, the shape of the opening d20 is preferably a concentric ring shape with the central opening of the winding processing surface 2. It is inferred that the two fluids are in rapid contact, suppressing the concentration distribution of the two fluids in the reaction field between the processing surfaces, and the mixing state becomes more uniform, so the progress of the precipitation reaction becomes more uniform, and the resulting pigment particles have the crystallite size and primary particle size. The diameter becomes more uniform.

This second introduction part d2 may have directivity. For example, as shown in FIG. 3(A), the introduction direction from 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 exceed 0 degrees and not reach 90 degrees. In addition, in the case of a fast reaction speed, it is preferable to set it to 1 degree or more and 45 degrees or less.

In addition, as shown in FIG. 3(B), the introduction direction from the opening d20 of the second processing surface 2 is one having directivity in a plane along the second processing surface 2. The introduction direction of this second fluid is the outer direction away from the center among the components in the radial direction of the processing surface, and is the positive direction in the components relative to the rotation direction of the fluid between the rotating processing surfaces. In other words, a line passing through the opening d20 in the radial direction, that is, the outer direction is divided into the reference line g, and the reference line g has a specific angle (θ2) from the reference line g to the rotation direction R. Regarding this angle (θ2), it is better to set it to exceed 0 degrees and not reach 90 degrees.

This angle (θ2) can be changed according to various conditions such as reaction speed, viscosity, and rotation speed of the processing surface. In addition, the second The introduction part d2 may not have directivity at all.

The number of the above-mentioned flow paths is two in the example of FIG. 1, but it may be three or more. In the example of FIG. 1, the second fluid is introduced between the processing surfaces 1 and 2 from the second introduction portion d2, but this introduction portion may be provided in the first processing portion 10 or both. In addition, it is possible to prepare a plurality of introduction parts for one type of fluid. In addition, the shape, size, or number of the openings for introduction provided in each processing portion are not particularly limited, and can be changed and implemented as appropriate. In addition, an opening for introduction may be provided directly before or on the upstream side between the first and second processing surfaces 1 and 2 described above.

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

[Pigment Dispersion]

In the present invention, a pigment dispersion can be obtained by putting the diketopyrrolopyrrole-based pigment particles of the present invention described above into an organic solvent of a dispersion medium and performing a dispersion treatment. The organic solvent is generally preferably an ester-based organic solvent. Here, the ester-based organic solvent used is not particularly limited, and a high boiling point organic solvent having a boiling point of preferably 100°C or higher, more preferably 110°C or higher, and still more preferably 130°C or higher is preferable. Such high boiling point organic solvents include ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethyl acetate Glycol monomethyl ether acetic acid 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 Ether acetate, diethylene glycol monobutyl ether acetate (BCA), etc.

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

Furthermore, if necessary, a dispersant may be added. The dispersant is not particularly limited. For example, when the main organic solvent is used, for example, carboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid (partial) amine salt, Polycarboxylic acid ammonium salt, polycarboxylic acid alkyl amine salt, polysiloxane, long-chain polyamino amide phosphate, polycarboxylic acid ester containing hydroxyl group or, these modifications, poly(lower alkylene) Amine) and a polyester having a free carboxylic acid group to form an amide or its salt; when it is mainly water-based, for example (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-( Meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins or water-soluble polymer compounds; sodium lauryl sulfate, polyoxyethylene alkyl ether Sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, dodecyl sulfuric acid Monoethanolamine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, polyoxyethylene Anion of base ether phosphate etc. Surfactant; polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol mono Nonionic surfactants such as lauric acid esters; Amphoteric surfactants such as alkyl dimethyl amino acetic acid betaine, alkyl betaines, alkyl imidazolines, etc., which can be used alone or in combination Used above.

Among these, dispersants having an amine structure in particular have excellent dispersibility and are suitable for use. Examples of such dispersants having an amine structure include the Solsperse series manufactured by Lubrizol, the Disperbyk series manufactured by BYK-Chemie, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto fine-techno. The amount of the dispersant is usually 100 parts by weight or less relative to 100 parts by weight of the pigment, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less.

In addition, a binder resin can be added at the same time as the dispersant. Binder resins include, for example, phenol resins, alkyd resins, polyester resins, amino resins, urea resins, melamine resins, guanamine resins, epoxy resins, styrene resins, vinyl resins, vinyl chloride resins, vinyl chloride/ Vinyl acetate copolymer resin, acrylic resin, polyurethane resin, silicone resin, polyamide resin, polyimide resin, rubber-based resin, cyclized rubber, maleinization oil-based resin , Butyraldehyde resin, polybutadiene resin, cellulose resin, chlorinated polyethylene, chlorinated polypropylene, etc. These binder resins can be used alone or in combination of two or more kinds. Binder resin can also be added when obtaining the photosensitive coloring composition mentioned later.

In addition, if necessary, compounds such as known pigment derivatives can also be added. These compounds are compounds that mediate the pigment and the dispersant. They are physically, electrically, and chemically adsorbed between the surface of the pigment and the dispersant, and have the function of improving dispersion stability. Such pigment derivatives include, for example, diketopyrrolopyrrole, anthraquinone, phthalocyanine, metal phthalocyanine, quinacridone, azo chelate, azo, and isoindole Phyrinone series, pyranthrone series, indanthrone series, anthracene pyrimidine series, dibromoanthanthrone series, flavanthrone series, perylene series, perylene series , Quinophthalone series, thioindigo series, dioxazine series and other organic pigments as the matrix, the introduction of hydroxyl, carboxyl, sulfonic acid, carbamido, sulfonamido and other substituents of the pigment derivative Things. Compounds such as these pigment derivatives can be used alone or in combination of two or more kinds.

The addition of these dispersants or binder resins, pigment derivatives and other compounds to the pigment dispersion helps reduce flocculation, improve the dispersion stability of the pigment, and improve the viscosity characteristics of the dispersion.

The above-mentioned dispersion treatment is not limited to the method or the disperser used in the treatment, but by adjusting the stirring speed or treatment time during the treatment, the pigment particles of the present invention can be dispersed even without excessive energy such as impact force. deal with. Therefore, it is also possible to use a stirring mechanism such as a ball mill, a bead mill, and a sand mill to vigorously stir a medium composed of glass, steel, stainless steel, ceramics, zirconium, zirconium dioxide, etc., to make the processed object Disperser, but even if it is not accompanied by the crushing of pigment particles Conditions can also be implemented. In addition, by using a dispersing machine that does not use the above-mentioned medium, the dispersion treatment is also possible. In this case, the same device as that used for the preparation of the pigment dissolving liquid or weak solvent can be cited. If it is not accompanied by the pulverization of pigment particles or even if it is accompanied by pulverization, the pulverization of the pigment particles is reduced, and the uniformity of the pigment particles after the dispersion treatment can be improved. As a result, it is advantageous to easily obtain effects that can help improve color characteristics.

[Photosensitive coloring composition]

At least a monomer and a photopolymerization initiator are mixed in the pigment dispersion to obtain a photosensitive coloring composition.

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

The photopolymerization initiator includes, for example, aromatic ketones, triarylimidazole dimers, benzidines, benzidine ethers, acetophenones, benzophenones, thioxanthones, acetals ( ketal), quinone, triazine, imidazole, oxime ester, phosphine, borate, carbazole, titanocene, polyhalogen, etc. Preferably, for example, 4,4'-bis(diethylamino)di Combination of benzophenone and 2-(o-chlorophenyl)-4, 5-diphenylimidazole dimer, 4-[pN, N-bis(ethoxycarbonylmethyl)-2, 6-dimer (Trichloromethyl)-s-triazine], 2-methyl-4'-(methylthio)-2-morpholinopropiophenone. These photopolymerization initiators can be used alone, or two or more of them can be mixed and used in any ratio if necessary.

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

Alkali-soluble resins that are generally used for negative resists can be used, as long as they are soluble in an aqueous alkali solution, they are not particularly limited. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Base) 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-decyl (meth)acrylate, benzyl (meth)acrylate , Styrene, γ-methylstyrene, N-vinyl-2-pyrrolidone, glycidyl (meth)acrylate, etc. with one or more selected from (meth)acrylic acid, itaconic acid, Copolymers composed of one or more of crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and these anhydrides, and the addition of an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group can also be mentioned. Polymers formed from the above-mentioned copolymers, etc. These alkali-soluble resins can also be added when the pigment dispersion is obtained as described above.

The photosensitive coloring composition of the present invention may also contain filler Additives such as additives, adhesion promoters, antioxidants, ultraviolet absorbers, flattening agents, etc.

[Color filter]

The photosensitive coloring composition containing the pigment microparticles of the present invention described above is coated on a substrate, photocured and developed to obtain a coating film, and a color filter can be manufactured. Hereinafter, this step is called the pre-baking step. Apply the photosensitive coloring composition on a substrate and attach it to a glass substrate or a silicon substrate, using a roll coater, slit coater, spray, coating bar, and coater (applicator), spin coater, dip coater, inkjet, screen printing coating is preferred. After coating, it is better to heat it from the viewpoint of the smoothness of the coating film or the handling of the organic solvent by drying. The heating temperature is preferably 50 to 140°C, more preferably 70 to 90°C, and the heating time is preferably 0.5 to 60 minutes, more preferably 1 to 10 minutes.

The light curing system irradiates the coating film with ultraviolet rays to harden the coating film. The photo-curing is performed in order to leave the pattern on the glass substrate by the subsequent development. For the part removed by the development, it is better to carry a UV-preventing photomask without curing. The photo-curing system is preferably carried out within the range of ^{10-100 mJ/cm 2 of ultraviolet radiation.} The development system immerses the hardened coating film after light hardening in an aqueous alkali solution, and then rinses with water to remove the unhardened part. In the aqueous alkali solution used, the concentration of the alkali agent is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight. In addition, 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, tetramethylammonium hydroxide, and the like.

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

The developed coating film is heated to 200~300°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 with excellent hardness can be formed. From the viewpoint of obtaining a cured film having excellent hardness and excellent heat resistance, the heating temperature is preferably 200 to 300°C. From the viewpoint of obtaining a cured film having excellent hardness and excellent heat resistance, the heating time is preferably 10 to 300 minutes. Before the post-baking step, it can also be pre-heated at 80~100°C for 10~60 minutes.

Example

Hereinafter, the invention of this case will be described in more detail with examples, but the invention of this case is not limited to these embodiments.

In addition, the symbols in the following examples indicate the following. In addition, the following weight% is described as wt%.

DMSO: dimethyl sulfide, NMP: N-methylpyrrolidone, TMAH aq.: 25wt% tetramethylammonium hydroxide aqueous solution, BTMA soln.: 40wt% benzyltrimethylammonium hydroxide methanol solution, EG: ethyl Diol, MeOH: methanol.

(Manufacturing of brominated diketopyrrolopyrrole)

1. In a stainless steel reaction vessel with a return tube for the generation of alkali metal salts of diketopyrrolopyrrole pigment compounds, in a nitrogen environment, add molecules 200 parts of tert-pentyl alcohol dehydrated by a molecular sieve and 140 parts of tert-pentyl alcohol sodium were heated to 100° C. while stirring to prepare an alcoholate solution. Next, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask, and the mixture was heated to 90°C to dissolve while stirring to prepare a mixture solution of these. The heated solution of this mixture was stirred vigorously, and dropped slowly at a constant speed over 2 hours into the alkoxide solution heated to 100°C. After the dropping was completed, 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

In addition, 600 parts of methanol, 600 parts of water, and 114 parts of acetic acid were added to a glass-made jacketed reaction vessel, and cooled to -10°C. Using a high-speed stirring disperser (DISPERSER) for the cooled mixture, while rotating a distribution disc with a diameter of 8 cm at 4000 rpm, a small amount of the alkali metal of the diketopyrrolopyrrole pigment compound obtained previously, which was cooled to 75°C, was added. Salt solution. At this time, while cooling, the temperature of the mixture of methanol, acetic acid, and water is always kept below -5°C, and the rate of adding 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 alkali metal salt solution was added, red crystals were precipitated, and a red suspension was obtained.

3. Separation and acquisition of brominated diketopyrrolopyrrole

Then, the obtained red suspension was packed with critical filtration at 5°C Set filter to obtain red paste. The paste was redispersed with 3500 parts of water at 25°C, washed, and filtered through a critical filter device for 3 times. The obtained water paste of the diketopyrrolopyrrole pigment compound was dried at 60°C for 72 hours, and then pulverized to obtain the brominated diketopyrrolopyrrole represented by the formula (III) (hereinafter referred to as "Bromo DPP") (the primary particle size observed by STEM described later is 40-60 nm) 150.8 parts.

Example 1

Pigment micronization

(Preparation of pigment solution)

As the solvent of the base material in Table 2, the DMSO 60wt% of raw material 1, add TMAH aq.28wt% of raw material 2, 9wt% brominated DPP, and EG 3wt% of raw material 4, using a high-speed rotary emulsifying disperser (m -Technique Co., Ltd., product name: CLEARMIX, hereinafter referred to as CLEARMIX) Stir to dissolve the brominated DPP. The prescription and preparation conditions are shown in Table 2 together with other Examples and Comparative Examples.

(Preparation of eco-solvent)

As a weak solvent, in 70wt% tap water of raw material 1 in Table 3, add 20wt% of citric acid of raw material 2 and EG 10wt% of raw material 4, and mix with CLEARMIX to prepare a weak solvent. The prescription and preparation conditions are shown in Table 3 together with other Examples and Comparative Examples.

(Precipitation of pigment particles)

It can be approached in the opposite configuration. At least one side of the separation is used in the thin film fluid formed between the processing surfaces 1 and 2 rotating relative to the other side, using uniform diffusion. Stir. The mixed reaction device mixes the finished pigment solution and the weak solvent, and continuously performs precipitation reaction in the thin film fluid. Specifically, the weak solvent as the first fluid is transported from the center of the device shown in FIG. 1 (the first introduction part d1), and the pigment solution is introduced as the second fluid into the processing surface 1 from the second introduction part d2. , 2 rooms. The first fluid and the second fluid are mixed in the thin film fluid to precipitate the pigment particles dissolved in the pigment dissolving liquid, and the pigment particle dispersion liquid is spit out from the processing surfaces 1, 2 Out. The supply pressure, flow rate and temperature of the first fluid and the second fluid, the number of revolutions of the processing part 10 (hereinafter referred to as the number of revolutions), the back pressure, and the temperature of the discharged fluid are used as the conditions for the production of pigment particles, and Other examples and comparative examples are shown in Table 4 together. The feeding temperature of the first fluid and the second fluid is measured by measuring the respective temperatures of the first fluid and the second fluid before being introduced into the device (more specifically, before being introduced between the processing surfaces 1 and 2), and the temperature of the discharged liquid is 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 uses a concentric ring shape with a central opening of the winding processing surface 2 as shown by the dotted line in FIG. 2(B).

(Wash and dry)

(a) In order to separate and obtain only the pigment fine particles in the pigment fine particle dispersion liquid discharged from the processing surface 1, 2 and slowly aggregate the pigment fine particles, filter the pigment fine particles by filtration under reduced pressure (-0.1MPaG) using filter paper.

(b) Put the obtained wet cake of pigment particles into 5L of tap water and stir with CLEARMIX at 6000rpm. After washing for 1.5 minutes, the operation of vacuum filtration and recovery of the washed liquid was repeated 4 times to obtain a wet cake of pigment particles. The obtained wet cake of pigment particles is vacuum dried to obtain a dry powder of pigment particles. The vacuum drying system was performed at 30°C and -0.10 MPaG for 72 hours.

For the obtained dry powder of pigment particles, X'PertPowder (manufactured by PANalytical) was used for X-ray diffraction measurement, and data analysis software HighScorePlus Ver.3.0e (3.0.5) (manufactured by PANalytical) was used. ) For analysis. In addition, ICP quantitative analysis is performed to measure the amount of Fe contained in the pigment particles.

Preparation of pigment dispersion

10 parts by weight of the resulting dry powder of pigment particles, "BYKLPN 6919" (manufactured by BYK-Chemie) as a dispersant, and CIpigment red 254 as a dispersion aid with a solid content of 5 parts by weight (hereinafter referred to as "BYKLPN 6919") 1 part by weight of the sulfonated derivative of R254"), 70 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") as a solvent, and mixed with a paint mixer (manufactured by Asada Iron Works Co., Ltd.) for 6 Disperse for hours to obtain a pigment dispersion of brominated DPP. Measure the viscosity of the resulting pigment dispersion. In addition, the obtained pigment dispersion was diluted with PGMEA and used as a dispersion liquid for STEM observation. The obtained dispersion liquid for STEM observation was dropped on the collodion film, and STEM observation was performed.

In addition, in order to adjust the chromaticity, a pigment dispersion of C.I. pigment red 177 (hereinafter referred to as "R177") was prepared. The pigment dispersion system of R177 uses 10 parts by weight of "CHROMOFINE RED A3B" (manufactured by BASF) as a pigment, and "BYKLPN6919" (manufactured by BYK-Chemie) as a dispersant with a solid content of 5 parts by weight as a dispersion 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 way as the preparation of the above-mentioned brominated DPP pigment dispersion.

Production of photosensitive coloring composition

Regarding the pigment dispersion of brominated DPP and the pigment dispersion of R177, the following production methods were used to produce respective photosensitive coloring compositions. 50 parts by weight of pigment dispersion, 6 parts by weight of acrylic resin ("ZAH-110" manufactured by Soken Chemical Co., Ltd.), 4 parts by weight of dipentaerythritol hexaacrylate as a polymerizable monomer, and 2 parts by weight as a photopolymerization initiator -Methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one ("IRGACURE 907" manufactured by BASF) 1 part by weight, 100 parts by weight of PGMEA as a solvent, after uniformly stirring and mixing, It was filtered with a 1.0 μm filter to obtain a photosensitive coloring composition.

Production of hardened film

The cured film is produced in the following two types. Using the photosensitive coloring composition of brominated DPP, in the post-baking step, set the chromaticity x=0.6500 to make a cured film with adjusted chromaticity, and evaluate coarse particles, contrast, film thickness, and heat resistance. Make Using the photosensitive coloring composition of brominated DPP and R177, in the post-baking step, the chromaticity x=0.6500 and y=0.3230 were used to prepare a cured film with adjusted chromaticity, and the brightness was evaluated.

1. Pre-bake steps

After coating the photosensitive coloring composition obtained above on a glass substrate with a spin coater, it dried at 80 degreeC for 3 minutes, and obtained the coating film. A photomask was placed on the obtained coating film, and an ultraviolet fiber spot (Fiber Spot) irradiation device was used to irradiate 100 mJ/cm ² of ultraviolet rays. In addition, it was shaken in an alkaline aqueous solution (0.04wt% potassium hydroxide aqueous solution), and then washed with pure water to remove the unhardened part. In addition, the number of rotations of the spin coater was changed to include the specified chromaticity, and 3 coating films were made, and the evaluation items of the specified chromaticity were calculated by the one-shot correlation method.

2. Post-baking steps

After removing the uncured part, the coating film was preliminarily heat-treated at 80°C for 30 minutes in a dryer, and then the main heat treatment was performed 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 production conditions of the pigment fine particles described in Table 4 were changed.

Example 3

Except for changing the formulation of the weak solvent described in Table 3, the same procedure as in Example 1 was carried out to obtain a cured film.

Example 4

Except for changing the production conditions of the pigment fine particles described in Table 4, the same procedure as in Example 1 was carried out to obtain a cured film.

Example 5

Except for changing the prescription of the pigment dissolving liquid described in Table 2, the same procedure as in Example 1 was carried out to obtain a cured film.

Example 6

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

Comparative example 1

In the comparative example without pigment microparticulation, the brominated DPP used as the pigment precursor in Examples 1 to 6 was not pigment microparticulated, and the pigment dispersion was prepared by the same method as in Example 1. The following is also the same to obtain a hardened pigment dispersion membrane.

Comparative example 2

Comparative Example 2 describes the color characteristics and primary particle size of pigment particles produced by pulverization and their changes. The production steps of the fine pigment particles of the pulverization method are performed following the well-known Japanese Patent Application Publication No. 2013-82905 in the literature of the salt pulverization method.

50 parts by weight of brominated DPP, 550 parts by weight of sodium chloride, and 110 parts by weight of diethylene glycol were put into the kneader, and kneaded by the salt milling method at 50° C. for 4 hours to produce a kneaded product of pigment fine particles.

In order to remove impurities from the resulting mixture of pigment particles, put the resulting mixture of pigment particles into 5L of tap water, use CLEARMIX, and stir at 6000rpm for 15 minutes. Washing, the cleaned liquid is filtered under reduced pressure (-0.1MPaG) using filter paper, and the pigment particles are collected by filtration. The wet cake of the pigment particles collected by filtration was washed in the same way as in Example 1. dry. Then, a pigment dispersion was prepared in the same manner as in Example 1, and the cured film was obtained in the same manner in the following.

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 the weak solvent prepared in Example 2 stirred at 1700 rpm using CLEARMIX to obtain a pigment fine particle dispersion. In order to separate and obtain only the pigment particles from the pigment particle dispersion liquid, and slowly agglomerate the pigment particles, use filter paper to filter and collect the pigment particles through reduced pressure filtration (-0.1MPaG). The wet cake of the collected pigment particles is combined with the filter paper. Example 1 was also washed. dry. Then, with real The pigment dispersion was prepared in the same manner as in Example 1, and the cured film was obtained in the same manner in the following.

Evaluation method

Measure the size of the crystallite by the aforementioned [Measurement of Crystallite Size], and then calculate the ratio of the crystallite size. In addition, the rate of change of interplanar spacing is calculated from the aforementioned [Rate of Interplanar Change of Lattice Plane]. Table 5 shows the results of these. In addition, the X-ray diffraction pattern of brominated DPP is shown in Figure 4. Compared with R254, the X-ray diffraction intensity is different, but the peak position appears in the same place. Therefore, it is assumed that the brominated DPP is the same as R254. The crystal structure and the crystal lattice plane of the crystal structure are analyzed. As mentioned 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 using the CIF data of the crystal structure, the calculation software Mercury can make the Bragg angle (2θ) correspond to the crystal lattice plane of the crystal structure.

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

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

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

For the above measurement results, if all the evaluations are ○, the total evaluation is ○.

Examples 1 to 6 satisfy that the crystallite size of the (1 1 1) plane is 140 Å or less, and the crystallite size of the (1 5 -1) plane is 80 Å or less, compared with the crystallites with the (1 1 1) plane In Comparative Examples 1 to 3 where the size exceeds 140 Å and the crystallite size of the (1 5 -1) plane exceeds 80 Å, the results of contrast and brightness are higher. This is by controlling the size of the crystallites to be small, so that the area of the crystal grain boundary is reduced and the light scattering is reduced, so the contrast and brightness of the resulting color filter are improved. In addition, by forming primary particles with small crystallites, the primary particles are made smaller, the transmittance of the color filter is high, and the light scattering is suppressed, which helps to improve the 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 average primary particle size is 5 to 40 nm in Examples 1 to 6, compared with those outside this range In Comparative Examples 1 to 3 of the ratio of the crystallite size and the average primary particle size, the results of higher contrast 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 a way with less anisotropy, and the primary particles become optically uniform. Improve contrast and brightness. In addition, the primary particles composed of nearly spherical crystallites also have a small aspect ratio and become difficult to align in the cured film, and the anisotropy of the cured film is reduced, which also contributes to the improvement of contrast and brightness. In addition, because the aspect ratio of the primary particles is small, the specific surface area of the pigment particles formed by the primary particles is small, and the surface energy of the particles is small, so the particles can be prevented from agglomerating. Even in the prior art, the high viscosity is caused by time. Fine pigments that increase viscosity or may cause gelation, but the brominated DPP pigment dispersion of the present invention can ensure dispersion stability.

The change rate of the (0 2 0) plane of the crystal lattice at 80°C and 230°C is less than 3.0% in Examples 1~6, compared to the comparative example 1~ in which the change rate of the surface spacing exceeds 3.0%. At 3 o'clock, higher heat resistance results are obtained. This is because the brominated DPP with a small rate of change of the interplanar spacing caused by heating shown in the embodiment has a specific crystallite size or a specific crystallite size ratio, so the crystal grain boundaries in the crystal structure can be suppressed from being small. The formation of crystallites is a tightly assembled stable crystal structure that can alleviate the decrease in contrast caused by heating. It can be seen from the above that by controlling various physical properties of brominated DPP, it is possible to obtain brominated DPP pigment particles that meet the characteristics required for color filters such as contrast, brightness, and heat resistance at a high level.

Example 7

Pigment micronization

(Preparation of pigment solution)

In Table 6, 65.5wt% of DMSO used as the solvent of the base material 1 is added with BTMA soln. 22.5wt% of the raw material 2, and 3 R254 of the commercially available pigment precursor (the primary particle size obtained by the aforementioned STEM observation is 100~120nm) 12wt%, use CLEARMIX to stir to dissolve R254. The prescription and preparation conditions are shown in Table 6 together with other Examples and Comparative Examples.

(Preparation of eco-solvent)

As a weak solvent, in 40wt% tap water of raw material 1 in Table 7, put 20wt% of acetic acid of raw material 2 and 40wt% of MeOH of raw material 3, and mix with CLEARMIX to prepare a weak solvent. The prescription and preparation conditions are shown in Table 7 together with other Examples and Comparative Examples.

(Precipitation of pigment particles)

It can be approached in the opposite configuration. At least one side of the separation is used in the thin film fluid formed between the processing surfaces 1 and 2 rotating relative to the other side, using uniform diffusion. Stir. The mixed reaction device mixes the finished pigment solution and the weak solvent, and continuously performs precipitation reaction in the thin film fluid. Specifically, the weak solvent as the first fluid is transported from the center of the device shown in FIG. 1 (the first introduction part d1), and the pigment solution is introduced as the second fluid into the processing surface 1 from the second introduction part d2. , 2 rooms. The first fluid and the second fluid are mixed in the thin film fluid to precipitate the pigment fine particles dissolved in the pigment dissolving liquid, and the pigment fine particle dispersion liquid is discharged from the processing surfaces 1 and 2. The supply pressure, flow rate and temperature of the first fluid and the second fluid, the number of revolutions of the processing part 10 (hereinafter referred to as the number of revolutions), the back pressure, and the temperature of the discharged fluid are used as the conditions for the production of pigment particles, and Other examples and comparative examples are shown in Table 8. The feeding temperature of the first fluid and the second fluid is measured by measuring the respective temperatures of the first fluid and the second fluid before being introduced into the device (more specifically, before being introduced between the processing surfaces 1 and 2), and the temperature of the discharged liquid is 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 uses a concentric ring shape with a central opening of the winding processing surface 2 as shown by the dotted line in FIG. 2(B).

(Wash and dry)

(a) In order to separate and obtain only the pigment fine particles in the pigment fine particle dispersion liquid discharged from the processing surface 1, 2 so as to gradually agglomerate the pigment fine particles, use a filter paper to filter and collect the pigment fine particles by filtration under reduced pressure (-0.1MPaG).

(b) Put the obtained wet cake of pigment particles into 5L of tap water and stir with CLEARMIX at 6000rpm. After washing for 1.5 minutes, the operation of vacuum filtration and recovery of the washed liquid was repeated 4 times to obtain a wet cake of pigment particles. The obtained wet cake of pigment particles is vacuum dried to obtain a dry powder of pigment particles. The vacuum drying system was performed at 30°C and -0.10 MPaG for 72 hours.

For the obtained dry powder of pigment particles, X'PertPowder (manufactured by PANalytical) was used for X-ray diffraction measurement, and data analysis software HighScorePlus Ver.3.0e (3.0.5) (manufactured by PANalytical) ) For analysis. In addition, ICP quantitative analysis is performed to measure the amount of Fe contained in the pigment particles.

Preparation of pigment dispersion

10 parts by weight of the resulting dry powder of pigment particles, "BYKLPN 6919" (manufactured by BYK-Chemie) as a dispersant, 5 parts by weight of solid content, and sulfonation of CIpigment red 254 as a dispersion aid 1 part by weight of propylene glycol monomethyl ether acetate as a solvent (hereinafter referred to as "PGMEA") 70 parts by weight, mixed with a paint mixer (manufactured by Asada Iron Works Co., Ltd.) for 6 hours of dispersion treatment to obtain R254 Pigment dispersion. In addition, the obtained pigment dispersion was diluted with PGMEA to obtain a dispersion liquid for STEM observation. The obtained dispersion liquid for STEM observation was dropped on the collodion film, and STEM observation was performed.

In addition, in order to adjust the chromaticity, a pigment dispersion of R177 was prepared in the same preparation method as described above.

Production of photosensitive coloring composition

Regarding the pigment dispersion of R254 and the pigment dispersion of R177, the following preparation methods were used to prepare respective photosensitive coloring compositions. 50 parts by weight of pigment dispersion, 6 parts by weight of acrylic resin ("ZAH-110" manufactured by Soken Chemical Co., Ltd.), 4 parts by weight of dipentaerythritol hexaacrylate as a polymerizable monomer, and 2 parts by weight as a photopolymerization initiator -Methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one ("IRGACURE 907" manufactured by BASF) 1 part by weight, 100 parts by weight of PGMEA as a solvent, after uniformly stirring and mixing, It was filtered with a 1.0 μm filter to obtain a photosensitive coloring composition.

Production of hardened film

The cured film is produced in the following two types. Using the photosensitive coloring composition of R254, in the post-baking step, set the chromaticity x=0.6500 to prepare a cured film with adjusted chromaticity, and evaluate coarse particles, contrast, film thickness, and heat resistance. Using the photosensitive coloring composition of R254 and R177, in the post-baking step, the chromaticity x=0.6500 and y=0.3230 were used to prepare a cured film with adjusted chromaticity, and the brightness was evaluated.

1. Pre-bake steps

After coating the photosensitive coloring composition obtained above on a glass substrate with a spin coater, it dried at 80 degreeC for 3 minutes, and obtained the coating film. A photomask was placed on the obtained coating film, and an ultraviolet fiber spot (Fiber Spot) irradiation device was used to irradiate 100 mJ/cm ² of ultraviolet rays. In addition, it was shaken in an alkaline aqueous solution (0.04wt% potassium hydroxide aqueous solution), and then washed with pure water to remove the unhardened part. In addition, the number of rotations of the spin coater was changed to include the specified chromaticity, and 3 coating films were made, and the evaluation items of the specified chromaticity were calculated by the one-shot correlation method.

2. Post-baking steps

After removing the uncured portion of the coating film in a dryer, preheating at 80°C for 30 minutes, and then performing a 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 production conditions 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 production conditions described in Table 8 were changed.

Comparative example 4

In the comparative example without pigment microparticulation, R254 used as the pigment precursor in Examples 7 to 9 was not pigment microparticulated, and the pigment dispersion was prepared by the same method as in Example 7. The cured film was obtained in the same manner below.

Comparative example 5

Except that the formulation of the weak solvent described in Table 7 and the production conditions of the pigment fine particles described in Table 8 were changed, the same procedure as in Example 9 was carried out to obtain a cured film. In addition, only tap water as a weak solvent is used, so CLEARMIX is not used to prepare a weak solvent.

Comparative example 6

Use a burette to add 350 mL of the pigment solution prepared in Example 8 at a speed of 35 mL/min. to the CLEARMIX and stir at 1700 rpm. In 1.1 L of the weak solvent prepared in Example 8, a pigment fine particle dispersion liquid was obtained. In order to separate and obtain only the pigment particles from the pigment particle dispersion liquid, and slowly agglomerate the pigment particles, use filter paper to filter and collect the pigment particles through reduced pressure filtration (-0.1MPaG). The wet cake of the collected pigment particles is combined with the filter paper. Example 7 was also washed. dry. Then, a pigment dispersion was prepared in the same manner as in Example 7, and the cured film was obtained in the same manner in the following.

The evaluation method system was performed in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 3, and the results are shown in Table 9. In addition, the judgment was also performed in the same manner as the judgment in Examples 1 to 6 and Comparative Examples 1 to 3.

Examples 7 to 9 satisfy that the crystallite size of the (1 1 1) plane is 140 Å or less, and the crystallite size of the (1 5 -1) plane is 80 Å or less, compared with the crystallites with the (1 1 1) plane In Comparative Examples 4 to 6, where the size exceeds 140 Å, and the crystallite size of the (1 5 -1) plane exceeds 80 Å, the results of contrast and brightness are higher. This is by controlling the size of the crystallites to be small, so that the area of the crystal grain boundary is reduced and the light scattering is reduced, so the contrast and brightness of the resulting color filter are improved. In addition, by forming primary particles with small crystallites, the primary particles are made smaller, the transmittance of the color filter is high, and the light scattering is suppressed, which helps to improve the 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 average primary particle size is 5 to 40 nm in Examples 7 to 9, compared with those outside this range In Comparative Examples 4 to 6 of the ratio of the crystallite size and the average primary particle size, results with higher contrast 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 a manner with less anisotropy, and the primary particles become optically uniform, which improves contrast and brightness. In addition, the primary particles composed of nearly spherical crystallites also have a small aspect ratio and become difficult to align in the cured film, and the anisotropy of the cured film is reduced, which also contributes to the improvement of contrast and brightness. In addition, because the aspect ratio of the primary particles is small, the specific surface area of the pigment particles formed by the primary particles is small, and the surface energy of the particles is small, so the particles can be prevented from agglomerating. Even in the prior art, the high viscosity is caused by time. Fine pigments that increase viscosity or may cause gelation, but the R254 pigment dispersion of the present invention can ensure dispersion stability.

The change of the plane spacing between the (0 2 0) plane of the crystal lattice at 80℃ and 230℃ In Examples 7 to 9 with a rate of 3.0% or less, compared with Comparative Examples 5 and 6 in which the rate of change of the interplanar spacing exceeds 3.0%, results with higher heat resistance were obtained. This is due to the fact that R254 has a specific crystallite size or a specific crystallite size ratio due to the small change rate of the interplanar spacing caused by heating as shown in the embodiment, so it can suppress the crystal grain boundaries in the crystal structure from being small and forming micro The crystals are densely assembled and stable crystal structures that can alleviate the decrease in contrast caused by heating.

From the above, it can be seen that by controlling the physical properties of the diketopyrrolopyrrole pigment particles, red pigment particles can be obtained that satisfy the characteristics required for a color filter such as contrast, brightness, and heat resistance at a high level.

Claims (19)

A type of diketopyrrolopyrrole pigment particles containing more than 90% of the compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern in the crystal lattice plane (±1 ±1 ±1 Among the 8 planes of ), the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is less than 140Å,

[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 Group or an aryl group which may have a substituent]. A type of diketopyrrolopyrrole pigment particles containing a compound represented by the following general formula (I), which are 8 of (±1 ±1 ±1) among the crystal lattice planes calculated by X-ray diffraction pattern Among the planes, the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is 140Å or less. The size of the crystallites 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 Group or an aryl group which may have a substituent]. A type of diketopyrrolopyrrole-based pigment particles containing a compound represented by the following general formula (I), which will be calculated from the X-ray diffraction pattern among the 8 planes of (±1 ±1 ±1), The size of the crystallite in the plane direction corresponding to the largest wave crest in the X-ray diffraction pattern is divided by the largest wave crest in the lattice plane calculated by the X-ray diffraction pattern and 2θ=3~10° The ratio of the crystallite size calculated by the corresponding surface direction of the crystallite size is 0.85~1.25, and the average primary particle size 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 Group or an aryl group which may have a substituent]. A kind of diketopyrrolopyrrole pigment particles containing more than 90% of the compound represented by the following general formula (I), which is a lattice calculated by X-ray diffraction pattern corresponding to 2θ=24.5°±0.3° The crystallite size of the surface is less than 140Å,

[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 Group or an aryl group which may have a substituent]. A type of diketopyrrolopyrrole pigment particles containing more than 90% of the compound represented by the following general formula (I), which is a crystal corresponding to 2θ=24.5°±0.3° calculated by X-ray diffraction pattern The crystallite size of the lattice plane is less than 140Å, and the crystallite size of the lattice plane corresponding to 2θ=28.0°±0.3° calculated by the X-ray diffraction pattern is less than 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 Group or an aryl group which may have a substituent]. Such as claim 1, 2, 4 or 5 diketopyrrolopyrrole pigment particles, wherein the average primary particle size is 5-40nm. A type of diketopyrrolopyrrole pigment microparticles containing a compound represented by the following general formula (I), which is calculated by X-ray diffraction pattern of the lattice plane corresponding to 2θ=24.5°±0.3° The ratio of the crystallite size divided by the crystallite size of the crystal lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern is 0.85~1.25, and the average primary particle size 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 Group or an aryl group which may have a substituent]. Such as the diketopyrrolopyrrole pigment particles of any one of claims 1 to 7, in which the surface of the lattice plane corresponding to the largest wave peak in 2θ=3~10° calculated by the X-ray diffraction pattern The rate of change of the interval between the value at 80°C and the value at 230°C (according to the following specific formula) is 3.0% or less, The rate of change between the value at 80℃ and the value at 230℃={(at 230 The surface interval at ℃)/(The surface interval at 80℃)×100}-100(%)[Specific formula] Such as the diketopyrrolopyrrole pigment microparticles of any one of claims 1 to 7, in which the plane spacing of the lattice plane corresponding to 2θ=7.4°±0.3° calculated by the X-ray diffraction pattern is The rate of change between the value at 80°C and the value at 230°C (according to the following specific formula) is 3.0% or less, The rate of change between the value at 80℃ and the value at 230℃={(plane interval at 230℃)/(plane interval at 80℃)×100}-100(%)[Specific formula] For example, the diketopyrrolopyrrole pigment particles of any one of claims 1 to 9, wherein the standard deviation of the primary particle size is less than 7.0. For example, the diketopyrrolopyrrole pigment particles of any one of claims 1 to 10, wherein the coefficient of variation (CV value) of the primary particle size is less than 30. Such as the diketopyrrolopyrrole pigment particles of any one of claims 1 to 11, wherein the content of Fe is 35 ppm or less. Such as the diketopyrrolopyrrole pigment particles of any one of claims 1 to 12, wherein the above general formula (I) is represented by the following general formula (II),

[In the above general formula (II), R is each independently representing 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, the diketopyrrolopyrrole pigment particles of claim 13, wherein R is bromine represented by the following formula (III),

A type of diketopyrrolopyrrole pigment particles containing the compound represented by the following formula (III), which are 8 of (±1 ±1 ±1) among the lattice planes calculated by the X-ray diffraction pattern Among the planes, the size of the crystallites in the plane direction corresponding to the largest peak in the X-ray diffraction pattern is less than 140 Å,

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 microparticle according to any one of claims 1-15. A photosensitive coloring composition containing at least diketopyrrolopyrrole-based pigment particles according to any one of claims 1 to 15. A color filter comprising at least the photosensitive coloring composition as claimed in claim 17. A color filter, which contains at least diketopyrrolopyrrole pigment particles according to any one of claims 1-15.

Images