WO2010032855A1

WO2010032855A1 - Fine particles of a water-insoluble compound, dispersion of same and process for production thereof

Info

Publication number: WO2010032855A1
Application number: PCT/JP2009/066456
Authority: WO
Inventors: 真人中尾; 大輔佐々木; 眞敏湯本; 敬太郎相見; 秀俊藤村; 陽介宮下; 敏貴二宮
Original assignee: 富士フイルム株式会社
Priority date: 2008-09-19
Filing date: 2009-09-18
Publication date: 2010-03-25

Abstract

Fine particles of a water-insoluble compound which are formed either by mixing a solution of a water-insoluble compound in a good solvent with a poor solvent with a dispersant dissolved in the good solvent and/or the poor solvent or by preparing a solution of a dispersant in a good solvent separately and mixing this solution with both a solution of a water-insoluble compound in a good solvent and a poor solvent and which contain the dispersant embedded therein, characterized in that the dispersant is embedded in the fine particles in an amount of 5 to 200mass% relative to the mass of the water-insoluble compound; and fine particles of a water-insoluble compound which are constituted of a water-insoluble compound and a dispersant, characterized in that at least 80mass% of the dispersant embedded in the fine particles is unevenly distributed in outside regions spreading from the surfaces of the fine particles to depths of 50% of the radii thereof.

Description

Fine particles of water-insoluble compound, dispersion thereof, and production method thereof

The present invention relates to fine particles of a water-insoluble compound suitably used for resists and inks formed on a substrate, a dispersion thereof, and a production method thereof.

If the pigment particles are made finer, the effect of light scattering is reduced and the light transmission is improved. For this reason, as a coloring material applied to an ink for inkjet recording or a pigment dispersion composition for a color filter, it is desired to make the pigment fine particles to 100 nanometers or less. Usually, the pigment is finely divided by a mechanical force using a disperser such as a sand mill, a roll mill, or a ball mill. However, it is difficult to make the pigment fine to the above size by this method. In addition, the smaller the particle size, the longer the dispersion takes, and the higher the cost, the more difficult it becomes to obtain a uniform quality.

On the other hand, a method (reprecipitation method) has been proposed in which a pigment is dissolved once and then precipitated again to form fine particles of the pigment. By using this reprecipitation method, it has become possible to form nanometer-order fine particles having excellent size uniformity. However, as the particles become finer, the particle surface area per unit mass of the particles increases cumulatively, and the fine particles tend to agglomerate rapidly. Therefore, it is extremely difficult to stably disperse particles in the nanometer region. On the other hand, if the amount of the dispersant used is simply increased, the dispersibility tends to increase, but the colorability and color purity are poor. In addition, since the dispersing agent is easily adsorbed on the surface of the particles, it can be easily detached. Therefore, storage of the fine particle dispersion or composition may cause particle aggregation or thickening. As a result, for example, when used as a paint or ink after storage, there are problems such as insufficient gloss and insufficient coloring power.

As an example of using a dispersant, an aqueous dispersion of pigment-containing particles is formed by mixing a pigment solution prepared by dissolving a dispersant and an organic pigment in an aprotic organic solvent in the presence of an alkali with water, and agglomerating the mixture. A fine pigment dispersion having a uniform size independent of the size of the primary particles of the pigment is disclosed by performing treatment and treatment for imparting redispersibility (see Patent Document 1). . As shown in FIG. 2, the obtained particles 30 have a structure in which the pigment (coloring material particles) 11 are included in the dispersant 22. With such a particle structure, when the particles are used as an ink liquid for ink jet recording, transparency, color density, storage stability, ink jet discharge durability and the like are excellent.

In addition, an attempt to attach a block copolymer to the surface of phthalocyanine pigment fine particles (Patent Document 2), an attempt to integrate a water-insoluble colorant and a chargeable resin pseudo particle (Patent Document 3), a polymer on the pigment particle surface An attempt to graft a chain (Patent Document 4) is disclosed. Although the predetermined effect is recognized by these, the particle formation process is complicated.

As an attempt to improve the dispersion stability, attempts have been made to improve the dispersion stability by chemically modifying the surface of the particles after forming the particles. For example, the surface of an organic pigment using a peroxide is hydrophilized and applied to an ink jet recording liquid (see Patent Document 5). A specific functional group is chemically bonded to the pigment surface via a diazo-based intermediate. Are disclosed (see Patent Document 6, etc.), and are shown to be excellent in long-term dispersion stability. However, in the method of directly chemically modifying these particles, the chemical modification cannot be made homogeneous unless the particles are sufficiently dispersed at a stage different from the chemical modification, and the reactivity of the chemical modification depends on the type of particle. Is not suitable for application to particles in the nanometer size region because it is difficult to occur and the chemical modification reaction is complicated.

JP 2004-43776 A JP 2005-314498 A JP 2004-331946 A JP 2007-327014 A Japanese Patent No. 2002-105352 US Pat. No. 5,554,739

In order to stably disperse particles in the nanometer size region, it cannot be said that the above-described conventional technology is still satisfactory. For example, there are many problems that need to be solved, such as requiring a large amount of a dispersant to be added, complicating the process with a chemical reaction, or imparting uniform dispersibility. It is desired to develop a technique that solves this problem and imparts good dispersibility as well as performance as a color material such as color and durability required for high-performance inks and precision optical elements.

By the way, as shown in FIG. 2, the particles of Patent Document 1 are said to have a structure in which pigment particles are incorporated into a polymer dispersant. However, since a considerable amount of the dispersant is liberated in the dispersion medium, it has been found that the dispersion stability is not sufficient (see Comparative Example 4 described later). In addition, although Patent Document 1 discloses a procedure for encapsulating particles in the polymer by polymerizing a polymerizable compound after forming colorant particles, it involves a chemical modification reaction. The particle formation process is complicated. Further, in any of these methods, since the colorant particles are covered with the dispersant, any improvement in the amount of the dispersant used is desired.

In view of the above points, an object of the present invention is to provide fine particles that are stably dispersed in a medium, and in particular, to provide fine particles of a water-insoluble compound excellent in dispersion stability with time and a dispersion thereof. The present invention also provides water-insoluble compound fine particles having the above-mentioned excellent characteristics that can be produced with a small amount of a dispersant by a simple particle formation step and, if necessary, a dispersion step without requiring complicated operations and special treatments. , Its dispersion, and its manufacturing method.

The above problems have been achieved by the following means.
(1) When mixing a solution in which a water-insoluble compound is dissolved in a good solvent and a poor solvent, (i) dissolving the dispersant on the good solvent side and / or the poor solvent side and mixing the two solutions, or (Ii) Apart from these, fine particles embedding the dispersant, prepared by preparing a solution in which the dispersant is dissolved in a good solvent and mixing with the two solutions,
Fine particles of a water-insoluble compound, wherein the dispersant is embedded in an amount of 5 to 200% by mass based on the mass of the water-insoluble compound.
(2) The fine particles according to (1), wherein 10% by mass or more and 100% by mass or less of the dispersant dissolved at the time of fine particle formation is taken in and embedded in the fine particles.
(3) The total amount of the dispersant dissolved in the good solvent and the poor solvent is 10 to 300 parts by mass with respect to 100 parts by mass of the water-insoluble compound, as described in (1) or (2) Fine particles.
(4) In the fine particles composed of a water-insoluble compound and a dispersing agent, 80% by mass or more of the dispersing agent embedded in the fine particles out of the dispersing agent has a particle radius from the particle surface of the fine particles. Fine particles of a water-insoluble compound characterized by being unevenly distributed in an outer region of up to 50%.
(5) When the fine particles are mixed with a poor solvent and a solution obtained by dissolving the water-insoluble compound in a good solvent, (i) the two liquids containing the dispersant on the good solvent side and / or the poor solvent side. Or (ii) a build-up fine particle embedding the dispersant, prepared by preparing a solution in which the dispersant is dissolved in a good solvent separately from these and mixing with the two solutions. Fine particles according to (4), characterized in that
(6) The fine particles according to (4) or (5), wherein the dispersant is embedded in an amount of 5 to 200% by mass based on the mass of the water-insoluble compound.
(7) The fine particles according to any one of (1) to (6), wherein the dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more.
(8) The fine particles according to any one of (1) to (7), wherein the dispersant is a polymer dispersant having at least one heterocyclic hydrocarbon group in the molecule.
(9) The dispersant is a polymer dispersant having a structural portion showing an interaction attracting the water-insoluble compound composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group. The fine particles according to any one of (1) to (8).
(10) The dispersant has at least one hydrophilic group selected from the group consisting of a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, an amide group, a sulfonamide group, and an alkylene oxide group. The fine particles according to any one of (1) to (9), wherein
(11) The dispersant further has a site having at least one bond selected from an ester bond, an ether bond, and an amide bond for dispersing the water-insoluble compound in a dispersion medium, or an aromatic ring. The fine particle according to (9) or (10), which is a polymer dispersant having a steric repulsive part having a repeating unit containing a part.
(12) The fine particles according to (11), wherein the steric repulsive portion of the embedded dispersant extends outward from the fine particles.
(13) The fine particles according to any one of (1) to (7), wherein the water-insoluble compound is a pigment.
(14) The good solvent is at least one solvent selected from the group consisting of an acidic solvent, an alkaline solvent, a polar organic solvent, and a supercritical fluid, or a mixture thereof. The fine particles according to any one of 13).
(15) The fine particles according to any one of (1) to (14), wherein the poor solvent is a solvent containing water as a main component.
(16) The fine particles according to any one of (1) to (15), wherein the average particle size is 100 nm or less.
(17) At least one selected from the group consisting of (a) an aqueous medium, (b) an organic solvent selected from an ester compound solvent, a ketone compound solvent, and an alcohol compound solvent, and (c) a reactive diluent. A fine particle dispersion of a water-insoluble compound, wherein the fine particles according to any one of (1) to (16) are dispersed in a solvent comprising a seed.
(18) The fine particle dispersion according to (17), which contains a dispersant not embedded in the fine particles.
(19) The fine particle dispersion according to (17) or (18), which is used for preparing a resist or ink formed on a substrate.
(20) For mixing a solution obtained by dissolving the water-insoluble compound in a good solvent and a poor solvent, (i) dissolving the dispersant on the good solvent side and / or the poor solvent side and mixing the both solutions, Or (ii) separately from these, in preparing a solution in which a dispersant is dissolved in a good solvent and mixing with both the liquids to produce fine particles of the water-insoluble compound,
A polymer dispersing agent having a structural part that exhibits an interaction attracting a water-insoluble compound is used as the dispersing agent, and 10% by mass or more and 100% by mass or less of the dispersing agent dissolved at the time of forming the fine particles is embedded in the fine particles. A method for producing fine particles of a water-insoluble compound.
(21) The dispersant is a polymer dispersant having a structural portion showing an interaction attracting the water-insoluble compound composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group. The method for producing fine particles according to (20).
(22) In producing a fine particle of the water-insoluble compound in which a solution obtained by dissolving a water-insoluble compound in a good solvent and a poor solvent are mixed to embed the dispersant, (i) the good solvent side and / or the poor solvent side Or the mixture of the two liquids, or (ii) preparing a solution in which the dispersant is dissolved in a good solvent separately from these, mixing the liquids together, and embedding them. A method for producing fine particles of a water-insoluble compound, wherein 80% by mass or more of the dispersant is unevenly distributed in an outer region from the particle surface of the fine particles to 50% of the particle radius.
(23) The dispersing agent comprises an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group, exhibiting an interaction property that attracts the water-insoluble compound, and the water-insoluble compound in the dispersion medium. It is a polymer dispersant having a steric repulsion part having a repeating unit containing at least one type of bond selected from an ester bond, an ether bond, and an amide bond for dispersion (22 ) Production method of the fine particles described in the above.

The fine particles of the water-insoluble compound of the present invention and the dispersion thereof have an excellent effect of suppressing aggregation of the fine particles in the dispersion medium and exhibit extremely good dispersibility even when the amount of the dispersant used is small. Play. Furthermore, the above-mentioned good dispersion state can be maintained over a long period of time, and it is possible to achieve both high dispersibility in a small amount of dispersant, which has been difficult in the past, and particularly high dispersion and storage stability over time. Can do. Further, according to the production method of the present invention, the water-insoluble compound fine particles having the above-mentioned excellent characteristics and the dispersion thereof can be easily formed without any complicated operation or special treatment, and if necessary, a dispersion step. Therefore, it can be produced with a small amount of dispersant, and can be suitably adapted to mass production for industrial use as a precision optical element material such as high-performance ink and color filter.

The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as appropriate.

Sectional drawing which shows typically the structure of the microparticles | fine-particles of 1st Embodiment of this invention. Sectional drawing which shows typically the structure of the microparticles | fine-particles of 2nd Embodiment of this invention. Sectional drawing which shows the structure of the conventional particle | grains (disclosed in patent document 1) typically

Hereinafter, preferred embodiments of the present invention will be described separately for the first embodiment and the second embodiment, but the present invention should not be construed as being limited thereto. The points common to both the embodiments will be described in the first embodiment.

[First Embodiment]
The fine particles of this embodiment embed a dispersant. Here, the term “embedding” refers to a state in which part or all of the molecules of the dispersing agent are taken into the fine particles. For example, referring to FIG. 1-1, the state in which all of the dispersant is incorporated is a state in which the entire molecule of the added dispersant is encapsulated in the fine particles 10 (see the embedded embedding dispersant 2b). The part-incorporated state is a state in which a part or functional group of the added dispersant is encapsulated in the particle and the remaining part extends outward from the particle (see the external embedding dispersant 2a). Both of these are included.

In the fine particles of the present embodiment, a specific dispersant coexists in at least one of a good solvent and a poor solvent, and a water-insoluble compound is dissolved in the good solvent together with or separately from the good solvent and the poor solvent side liquid. And build-up fine particles in which the dispersant is embedded in the particles. The dispersant is preferably a polymer dispersant having a mass average molecular weight of 1000 or more, and more preferably a polymer dispersant having a specific structural site as described later.

In this embodiment, the dispersing agent partially or wholly incorporated into the inside of the particle is not simply merely physically adsorbed on the particle surface as in the prior art, but is immobilized and irreversibly incorporated within the particle. For this reason, unless the fine particles are destroyed or dissolved, the dispersion medium and / or the composition solvent usually does not release or desorb. Therefore, the fine particles embedded with the dispersant have a high dispersion effect that the aggregation of the particles can be suppressed, and the dispersion stability is extremely high even if the amount of the dispersant used is small. The characteristics of the fine particles embedded with the dispersing agent of this embodiment can be confirmed by measuring the amount of the dispersing agent that does not desorb even after repeated washing with a solvent in which the dispersing agent dissolves. .

The method for efficiently embedding the dispersing agent in the particles is not particularly limited. For example, a specific dispersing agent can be selected and used, or by adjusting process conditions such as a channel mixing method. . Below, the preferable embodiment which embeds a dispersing agent in particle | grains is demonstrated in detail.

In order to embed the dispersant in the particles by the usual reprecipitation method, it is preferable to use a specific dispersant. At this time, if all the dispersant molecules are encapsulated in the particles and all the functional groups necessary for the dispersion are also encapsulated in the particles, it may not be possible to sufficiently fulfill the role of imparting the dispersibility of the dispersant. Therefore, it is preferable that all the functional groups necessary for the dispersion are not included in the particles. In order to appropriately encapsulate the dispersant in the fine particles and impart dispersion stability, it is preferable to use a dispersant that satisfies the following requirements. That is,
(1) The medium in which the dispersant can be dissolved is compatible with the medium in which the water-insoluble compound used in combination can be dissolved;
(2) The dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more,
(3) The dispersant is precipitated by mixing with a poor solvent, but the deposition rate is slower than the precipitation of the water-insoluble compound.
(4) The dispersant contains at least one functional group having an interactive property attracting a water-insoluble compound,
By achieving the above requirements, the dispersant can be efficiently and moderately encapsulated in the particles.

The dispersant to be embedded used in the present embodiment is preferably used after being dissolved in a good solvent for dissolving the water-insoluble compound, a good solvent prepared separately from this, or a poor solvent. The following method is mentioned as a preferable embodiment of dissolution and mixing of the dispersant.
(1) A method in which a dispersant is co-dissolved in a good solvent together with a water-insoluble compound, brought into contact with a poor solvent, and precipitated. (2) A water-insoluble compound solution and a dispersant solution are prepared separately. (3) A method in which a solution obtained by dissolving a dispersant in a water-insoluble compound solution and a poor solvent is brought into contact with each other to cause precipitation.
The fine particles of the present invention may be prepared by any of these methods, but it is preferable that the dispersant-dissolved solution is compatible with the water-insoluble compound solution. If the dispersant solution and the water-insoluble compound solution are not compatible with each other, the dispersant may not be sufficiently incorporated into the particles by mixing with the poor solvent. Among the above methods, the methods (1) and (2) are particularly preferably used.

In the present embodiment, in order to incorporate the dispersant into the particles, the dispersant is preferably a polymer dispersant having a mass average molecular weight of 1000 or more, more preferably 3000 to 300,000, and particularly preferably It is 5000 or more and 100,000 or less. If the molecular weight of the dispersant is too low, the proportion of the dispersant incorporated into the particle may decrease, and if it is too large, aggregation of the dispersant may increase and redispersibility may deteriorate. The dispersion of the dispersant is preferably narrow, that is, monodisperse. The degree of dispersion of the dispersant is represented by a ratio of the number average molecular weight to the mass average molecular weight, and a dispersant having a dispersity in the range of 1.0 to 5.0 is preferable, and a range of 1.0 to 4.0 is particularly preferable. Is used.

The dispersant embedded in the fine particles used in the present embodiment (hereinafter, sometimes referred to as “embedding dispersant” to be distinguished from a simple dispersant) is dissolved in a solvent in advance and mixed with a poor solvent. It can be made to precipitate. Similarly, a water-insoluble compound can also be dissolved in a good solvent and precipitated by contact with a poor solvent to form fine particles. In such a fine particle formation stage, when the deposition rate of the dispersant is faster than the deposition rate of the water-insoluble compound, the dispersant is deposited before it is sufficiently incorporated into the particles, so that the dispersant is incorporated into the particles. Hateful. In order to sufficiently incorporate the dispersant into the particles, it is preferable that the deposition rate of the dispersant is lower than the deposition rate of the water-insoluble compound. And the state which takes in this dispersing agent in microparticles | fine-particles can be controlled by adjusting the deposition rate of the embedding dispersing agent in this way as needed. From the viewpoint of incorporating the dispersant into the fine particles as in the above eutectic, the deposition rate of the embedding dispersant is preferably slower than that of the water-insoluble compound. Depending on the affinity between the insoluble compound and the dispersant, the precipitation rate of the water-insoluble compound, the structure of the dispersant, the solvent affinity between the good solvent and the poor solvent, etc., the precipitation rate ratio between the water-insoluble compound and the dispersant is determined for each particle. It is preferable to determine based on formation conditions.

Next, the structure and the action of a preferable dispersing agent for incorporating the embedding dispersant into the particles and further preventing the embedded dispersing agent from being released in the dispersion medium or the composition medium will be described.
In order to embed the embedding dispersant appropriately in the particles, the chemistry of the embedding dispersant is shown so that the dispersing agent and the water-insoluble compound are precipitated through a mixing process so as to exhibit an attractive interaction between them. It is preferable to design the structure. In the present invention, it is preferable to mix the embedding dispersant and the water-insoluble compound in a state dissolved in a solvent. At this time, if the interaction between the dispersant and the water-insoluble compound is small, In some cases, the incorporation rate into the composition may be too small, or the embedded dispersant may be easily released in the dispersion medium or the composition medium, or the dispersion stability may deteriorate. For this reason, it is preferable to use an embedding dispersant having a structure site that strongly attracts and interacts with the water-insoluble compound, and it is preferable to strengthen this interaction to enhance entrainment and firmly fix the dispersant to the particles.

In the microparticles of the present embodiment, it is preferable that 10% by mass or more of the embedding dispersant introduced into the system at the time of microparticle formation is embedded. That is, with respect to the mass (A) of the added embedding dispersant, the percentage of the mass (B) of the dispersant incorporated and embedded in the particles ((B) / (A) × 100) ( Hereinafter, this rate may be referred to as “dispersing agent uptake rate.”) Is preferably 10% by mass or more. Further, the dispersant uptake rate ((B) / (A)) is more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Although there is no particular upper limit on the dispersion uptake rate, the upper limit in calculation is 100% by mass, and it is practical that it is 98% by mass or less. In the present invention, the measurement and calculation of the above-mentioned “dispersing agent uptake rate” is performed according to the method described in the following examples unless otherwise specified.

The fine particles of the present embodiment have extremely high dispersion stability over time as well as initial dispersibility because a larger amount of dispersant is incorporated into the particles than ever before. Needless to say, the amount of the dispersant used can be reduced, the manufacturing cost can be reduced, and unnecessary dispersant components can be greatly reduced by switching the solvent, which is excellent in environmental compatibility.

The amount of the embedded embedding dispersant is assumed to be the ratio of the fine particles to the mass of components other than the dispersant, that is, the embedding dispersant forming the fine particles as a dispersed phase and the continuous phase formed by a water-insoluble compound or the like. Sometimes the percentage of the ratio of the mass (X) of the embedding dispersant constituting the dispersed phase to the mass (Y) of the continuous phase of the fine particles ((X) / (Y) × 100) (hereinafter this ratio is (It may be referred to as “dispersing agent embedding ratio”). It is 5 to 200% by mass (this point is optional in the second embodiment), and more preferably 8 to 160% by mass. preferable. The measurement and calculation of the “dispersing agent embedding rate” is performed according to the method described in the following examples unless otherwise specified.

[Second Embodiment]
The fine particle of the present embodiment is a fine particle composed of a water-insoluble compound and a dispersant, and is 50% of the particle radius from the particle surface (this ratio is determined from the particle surface of the particle radius line to the inside of the particle). This is the percentage of the value obtained by dividing the distance to the fixed point by the distance (radius) from the particle center to the particle surface, and corresponds to the percentage of [radius outside distance r ₂ / radius R] shown in FIG. When the particle is not a sphere, the distance from the approximate center point of the particle to the outer surface can be regarded as the radius, which will be described in detail later). 80% by mass or more of the dispersing agent embedded in is unevenly distributed. Here, embedding means a state in which a part or all of the components of the dispersant are taken into the particles. For example, referring to FIG. 1-2, the state in which all of the dispersant is incorporated is a state in which the entire molecule of the added dispersant is encapsulated in the particles 20 (see the embedded embedding dispersant 2b). The partially incorporated state is a state in which a part of the added dispersant or a functional group is encapsulated in the particle and extends to the outside of the remaining particle (see the embedded embedding dispersant 2a). Sometimes both are included. The uneven distribution in the particle outer region Ao means a state in which almost no dispersant is encapsulated in the vicinity of the center of the particle and most of the dispersant is encapsulated only in the vicinity of the particle surface. . The distribution of the unevenly distributed dispersant of the present invention is defined by an outer region Ao within 50% (r ₂ / R) of the particle radius from the particle surface, preferably 40% (r ₂ / R of the particle radius from the particle surface). R) is defined by the outer region Ao within the range, and more preferably is defined by the outer region Ao within 30% (r ₂ / R) of the particle radius from the particle surface.

In this embodiment, measurement of the distribution of uneven distribution and dispersion agent inside the particles, although such a transmission electron microscope and nuclear magnetic resonance spectra are mentioned, a particularly suitably measured using a solid ^{13 C} CP / MAS NMR is there.

The fine particle preparation relating to the uptake of the dispersant, the definition of the uptake rate and the embedding rate, the measurement / calculation method, and the preferred range are the same as in the first embodiment.

(Embedding dispersant)
The interaction that attracts the embedding dispersant or a water-insoluble compound that is preferable as a structural site thereof means an interaction between molecules or between the structural sites in terms of adsorptivity or affinity, specifically hydrogen bonding interaction. , Π-π interaction, ion-ion interaction, dipole interaction, London dispersion force (Van der Waals force), and charge transfer interaction. Other examples include hydrophobic interaction based on thermodynamic factors. Any of the above-described interactions may be used as the interaction between the dispersant or the structural site thereof and the water-insoluble compound, and is not particularly limited, but in particular, hydrogen bonding interaction, π-π interaction, ion It is effective that it is an interaction. Therefore, it is preferable to introduce a site exhibiting the above-mentioned interaction as a partial structure of the embedding / dispersing agent, whereby the dispersing agent is easily taken into the particles and easily embedded.

In the following, embodiments of hydrogen bond interaction, π-π interaction, and ion-ion interaction are taken as examples, and the molecular structure and design of the dispersant for imparting these interactions are described.

The hydrogen bond interaction occurs in a molecule in which hydrogen is covalently bonded to an atom having high electronegativity such as fluorine, oxygen, or nitrogen, and in this case, a polar molecule is generated. At this time, the hydrogen atom is charged to a positive charge smaller than 1, and as a result, an interaction occurs when an attempt is made to adsorb a negatively charged atom such as oxygen contained in another nearby molecule. This results in a stable bond that connects the two molecules. For example, when a dispersant having a functional group that easily causes the above-described interaction via a hydrogen bond with a water-insoluble compound is used, the incorporation rate of the dispersant into the fine particles can be increased.

Π-π interaction is a dispersion force acting between aromatic rings of organic compound molecules, and is also called stacking interaction. For example, aromatic compounds have a strong planar structure and abundant electrons delocalized by the π-electron system, so that the London dispersion force is particularly strong. Therefore, the force attracting each other increases as the number of π electrons increases. For example, when a dispersant having a functional group that easily interacts with a water-insoluble compound and π-π can be used, the incorporation rate of the dispersant into the fine particles can be increased.

The ion-ion interaction is an interaction that occurs between charged ions. For example, since different charges attract each other, if the molecular design is such that the dispersant has a charge different from that of the water-insoluble target substance in the dispersion medium, the interaction between the dispersant and the water-insoluble compound is enhanced, The uptake rate into the fine particles can be increased.

In the present invention, it is preferable to use a material in which the embedding dispersant and the water-insoluble compound are molecularly designed so as to exhibit the plurality of interactions described above. The preferred molecular structure of the dispersant varies depending on the type of the water-insoluble compound of interest. For example, when the water-insoluble compound is an organic pigment, it has a heterocyclic moiety in order to impart a hydrogen bonding interaction. A polymer compound can be preferably used, and a polymer compound having a nitrogen-containing heterocyclic moiety is particularly preferred. Furthermore, a dispersant having an aromatic ring as a partial structure is preferable in order to impart π-π interaction or hydrophobic interaction. Moreover, what has a heterocycle and an aromatic ring simultaneously in the same molecular skeleton is especially preferable.

Specific examples of the heterocyclic partial structure of a preferable dispersant used in the present invention include the following sites (I-1) to (I-29), phthalocyanine-based, insoluble azo-based, azo lake-based, anthraquinone-based, quinacridone-based Organic dye structures such as dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, and the like in the present invention. It is not limited to. The unit having these sites is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. Particularly preferably, it is introduced in the range of 0 to 90.0 mol%.

In addition, as the dispersant used in the present invention, a dispersant having the following sites (II-1) to (II-4) can be used for the purpose of interaction between ions, but it is particularly limited to these. It will never be done. The unit having these sites is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. Particularly preferably, it is introduced in the range of 0 to 90.0 mol%.

The embedding / dispersing agent is preferably a polymer compound having the above-described interaction group in a partial structure, but further includes an organic solvent medium (for example, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent). Preferable examples include solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, nitrile solvents, and mixtures thereof. Among them, ketone solvents, ether solvents, ester solvents An aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a mixture thereof is more preferable, and examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and the like. Examples of the solvent include propylene glycol monomethyl ether and propylene glycol. Examples include ester solvents such as 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. , Ethyl lactate, butyl acetate, ethyl carbitol acetate, butyl carbitol acetate, etc. Examples of the aromatic hydrocarbon solvent include toluene, xylene, etc. Examples of the aliphatic hydrocarbon solvent include , Cyclohexane, n-octane, etc. These solvents may be used alone or in combination of two or more, and a solvent having a boiling point of 180 ° C. to 250 ° C. may be used if necessary. Or reactive diluent (eg 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, N-vinyl- It is also preferred that the dispersion medium such as 2-pyrrolidone, N-acryloylmorpholine, etc.) also has a partial structure (affinity site) with high affinity. Due to the affinity, dispersibility can be imparted in the dispersion medium by the portion (2o site in FIG. 1-1) of the embedding dispersant outside the particles.

The affinity site with the dispersion medium is not particularly limited, but examples of the type (s) of the compound include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid. Preferred examples include diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (meth) acrylate, phenyl (meth) acrylate , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2- (Ethoxyethyl) (meth) acrylate, 2- (2-methoxyeth) (meth) acrylate B) ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) Vinyl acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meta ) Acrylic acid benzyl, (meth) acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) Ak Polyethylene glycol monomethyl ether, polyethylene glycol monoethyl (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth ) Dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) Examples thereof include tribromophenyl acrylate, tribromophenyloxyethyl (meth) acrylate, and γ-butyrolactone (meth) acrylate.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.

Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N-methylo Le acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

Examples of olefins include ethylene, propylene, isobutylene, butadiene, and isoprene.

Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

(Meth) acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinylcaprolactone, etc. can also be used.

Next, the structure of the preferable dispersing agent and its function for allowing the embedding dispersant to be incorporated into the particles and for the incorporated dispersing agent to be unevenly distributed in the outer region of the particles will be described.
In order to make the embedding dispersant unevenly distributed in the vicinity of the particle surface, it is preferable to use an embedding type dispersing agent having a steric repulsive site having a repeating unit in addition to the above-mentioned interactive group.
In the present invention, it is preferable to mix the embedding dispersant having the above-described interacting structural site and the water-insoluble compound in a state dissolved in a solvent. At this time, the encapsulated dispersant has a steric repulsive site. Otherwise, a water-insoluble compound is newly deposited on the incorporated dispersant, and as a result, fine particles are obtained in which the embedding dispersant is incorporated into the center of the particle. Therefore, the above-described interacting structural part for incorporating the embedding dispersant into the particles and the structural part having a steric repulsive action having a repeating unit so that a new water-insoluble compound does not precipitate on the incorporated dispersing agent. It is preferable to have both.

The embedding dispersant is preferably a polymer compound having the above-mentioned interaction group and steric repulsion group in a partial structure, but the portion having steric repulsion is a dispersion medium and / or composition medium is an organic solvent-based medium. (For example, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, nitrile solvents, or mixtures thereof, etc. Among them, a ketone solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a mixture thereof is more preferable. Examples include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Examples of ether solvents include Examples include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. Examples of ester solvents include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Examples include ethyl ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl carbitol acetate, butyl carbitol acetate, etc. Examples of aromatic hydrocarbon solvents include toluene, xylene, and the like. Examples of the group hydrocarbon solvent include cyclohexane, n-octane, etc. These solvents may be used alone or in combination of two or more, and have a boiling point of 180 ° C. to 250 ° C. is there Or reactive diluents (eg 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl) (Meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polymerizable compounds such as N-vinyl-2-pyrrolidone, N-acryloylmorpholine) are preferred. Since the steric repulsion part has an affinity for the dispersion medium, the steric repulsion part has both the effect of unevenly distributing the embedding dispersant in the outer region of the particle and the effect of dispersing the particle in the dispersion medium. Therefore, good dispersibility can be exhibited with a smaller amount of dispersant.

In the present invention, the embedding dispersant that is unevenly distributed in the outer region of the particle tends to reduce the proportion of the steric repulsion site that contributes to the dispersion into the particle, and the steric repulsion site contributes to the dispersion effectively. sell. Therefore, compared with the case where the dispersant is taken up to the center of the particle, the dispersibility is extremely high even if the amount of the dispersant used is small, which is preferable. Of the steric repulsion sites of the dispersant embedded in the fine particles, the mass of the portion (2o in FIG. 1) extending outward from the fine particles with respect to the mass (P) of the steric repulsion sites of the dispersant 2 The percentage of (O) ((O) / (P) × 100) (hereinafter, this rate is referred to as “outward extension rate”) is preferably 40 to 100% by mass. If the above-mentioned outward extension ratio indicating the degree to which the steric repulsion chain of the embedding dispersant is exposed to the outside of the particle is small, the ratio of the steric repulsion chain that can contribute to the dispersion becomes small, and the dispersibility of the fine particles immediately after dispersion is reduced. May not be enough. Further, the outward extension ratio is more preferably 50 to 100% by mass, and particularly preferably 60 to 100% by mass. Although there is no particular upper limit for the outward extension rate, the upper limit for calculation is 100% by mass, and it is practical that it is 99% by mass or less. In the present invention, the dispersant uptake rate is determined according to the method described in the following examples unless otherwise specified.

The steric repulsive part is preferably composed of a repeating unit including a part having at least one bond selected from an ester bond, an ether bond and an amide bond, or a part having an aromatic ring. Examples of the structural moiety composed of the repeating unit constituting these steric repulsive dispersing groups include the following (III-1) to (III-5), but are not particularly limited in the present invention. . The steric repulsive structural portion is preferably 1.0 to 99.0 mol%, more preferably 3.0 to 95.0 mol% of the entire unit constituting the polymer compound. It is particularly preferable to introduce in the range of 0.0 to 90.0 mol%. In the formula, m is preferably 3 to 200, and more preferably 5 to 120.
These steric repulsive sites may be used alone or in combination of two or more.

Among these, the other functional group is more preferably a vinyl monomer polymer or copolymer having a hydrocarbon group having 4 or more carbon atoms, and more preferably a hydrocarbon having 6 to 24 carbon atoms. Particularly preferred is a polymer or copolymer of a monomer having a group. Preferable examples of the other functional groups include functional groups obtained by polymerizing the monomers u-1 to u-12.

Furthermore, a monomer containing an ionic functional group can be used. Among the ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers), as the anionic vinyl monomer, alkali metal salts of vinyl monomers having the acidic group, organic amines (for example, triethylamine, dimethylaminoethanol, etc.) And the like. As the cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom): Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkylesters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1— 18); dialky sulfate (Alkyl group: C1 ~ 4) that is quaternized with such, like dialkyl diallyl ammonium salts.

The fine particles of the present invention can also be used as a colorant for inkjet recording ink. In this case, the main component of the dispersion medium and / or the composition medium is an aqueous solvent (for example, water and a water / water-soluble organic solvent mixture. Examples of the water-soluble organic solvent include glycerin, 1,2,6-hexanetriol, Trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2 Alkanediols such as methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol (polyhydric alcohols) ); Glucose, Mannose, Fructose, Ribo Sugars such as xylose, arabinose, galactose, aldonic acid, glucitol, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose; sugar alcohols; hyaluronic acids; so-called solid wetting agents such as ureas; ethanol, methanol, butanol Alkyl alcohols having 1 to 4 carbon atoms such as propanol and isopropanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- n-propyl ether, ethylene glycol mono-iso-propyl ether , Diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl Ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether Glycol ethers such as dipropylene glycol mono-iso-propyl ether; 2 -Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, formamide, acetamide, dimethyl sulfoxide, sorbitol, sorbitan, acetin, diacetin, triacetin, sulfolane, etc., one of these Or 2 or more types can be used.
Polyhydric alcohols are useful for the purpose of drying inhibitors and wetting agents. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, tetraethylene glycol, 1,6-hexanediol, 2-methyl-2, Examples thereof include 4-pentanediol, polyethylene glycol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like. These may be used singly or in combination of two or more), and it is possible to suppress aggregation between fine particles by electrostatic repulsion, and the acidity By introducing a group, basic group, or ionic functional group, dispersion in an aqueous medium becomes possible.

The form of polymerization of the embedding dispersant having the interaction group, the steric repulsion dispersing group, and various functional groups is not particularly limited, but the unit having the interaction group, the unit having the steric repulsion dispersion group, various types Polymers or copolymers of vinyl monomers in units having functional groups (for example, alkyl methacrylate homopolymers, styrene homopolymers, alkyl methacrylate / styrene copolymers, polyvinyl butyral, etc.) , Ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amide polymers (eg, Polyamide 6 and polyamide 66 ), Silicone polymer (e.g., polydimethylsiloxane, etc.), carbonate-based polymers (e.g., polycarbonate synthesized from bisphenol A and phosgene), and the like.

Among these, the polymer compound is preferably a polymer or copolymer of each vinyl monomer, an ester polymer, an ether polymer, or a modified product or copolymer thereof. From the viewpoint of adjusting solubility in a solvent, cost, ease of synthesis, etc., the polymer compound is most preferably a polymer or copolymer of each vinyl monomer.

For the production of the polymer or copolymer of each vinyl monomer, for example, a method by radical polymerization can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.

The polymer dispersant used as the embedding dispersant can be used in any binding form. Specifically, any (co) polymers of random (co) polymers, block (co) polymers, and graft (co) polymers can be used. In particular, block (co) polymers, grafts (Co) polymers are preferred.

The fine particles of the water-insoluble compound of the present invention are preferably those in which the embedding dispersant having the above specific structure site is mainly used and embedded in the fine particles, but a non-embedded dispersant may be used in combination. . Dispersant used in combination, for example, viscosity adjustment of the dispersion, photodevelopment imparting, reactivity with the embedding dispersant, interaction with the embedding dispersant, affinity with the dispersion medium, It can be used for the purpose of deaggregating particles precipitated in a poor solvent, the purpose of adjusting the size of fine particles, the purpose of adjusting the affinity between a good solvent and a poor solvent, and the purpose of imparting affinity to a dispersion medium. Ordinary dispersants such as surfactants, low molecular dispersants and polymer dispersants can be used in combination. The use ratio and the number of the dispersant used in combination are not particularly limited, but it is preferably used in the range of 0.01 to 195% by mass with respect to 1% by mass of the water-insoluble compound. It is more preferable to use in the range of mass%. Furthermore, the number of dispersants used in combination is preferably one or more.

As the dispersant used in combination, a polymer compound can be used. Specifically, styrene, styrene derivatives, vinyl naphthalene, vinyl naphthalene derivatives, aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acid, acrylic acid, etc. , Acrylic acid derivative, methacrylic acid, methacrylic acid derivative, maleic acid, maleic acid derivative, alkenyl sulfonic acid, vinylamine, allylamine, itaconic acid, itaconic acid derivative, fumaric acid, fumaric acid derivative, vinyl acetate, vinylphosphonic acid, vinylpyrrolidone , Acrylamide, N-vinylacetamide, N-vinylformamide and derivatives thereof, etc. (of which at least one is a carboxylic acid group, sulfonic acid group, phosphoric acid group, hydroxyl group, alkylene) Any of the oxides A block copolymer composed of a monomer having a functional group), a random copolymer, a graft copolymer, a modified product thereof, a salt thereof, and the like. Alternatively, natural polymer compounds such as albumin, gelatin, rosin, shellac, starch, gum arabic and sodium alginate, and modified products thereof can be used in combination.

(Non-embedding dispersant)
It is preferable to use the following specific polymer compounds A to D as dispersants that are used in combination with the embedding dispersant and are not embedded in the fine particles of the water-insoluble compound. The more preferable range in is described individually if necessary), but is preferably from 1,000 to 500,000, more preferably from 2,000 to 300,000, and particularly preferably from 3,000 to 200,000. In the present invention, the molecular weight and the degree of dispersion are determined by the methods measured in the examples unless otherwise specified.

[Polymer Compound A]
In this embodiment, a polymer compound having a heterocyclic ring in the side chain is preferable. Such a polymer compound is preferably a monomer represented by the following general formula (1) or a polymer containing a polymer unit derived from a monomer comprising a maleimide or a maleimide derivative. A polymer containing a polymer unit derived from the monomer represented by the general formula (1) is particularly preferable.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents a single bond or a divalent linking group. Y represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic structure.
The alkyl group for R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ¹ has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms). A methoxy group, an ethoxy group, a cyclohexyloxy group, etc. are mentioned.

Specific examples of preferable alkyl group represented by R ¹ include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-methoxyethyl group.
R ¹ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R ² represents a single bond or a divalent linking group. The divalent linking group is preferably a substituted or unsubstituted alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
^Two or more alkylene groups represented by R ² may be linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom).
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the preferable alkylene group represented by R ² has a substituent, examples of the substituent include a hydroxy group.

Examples of the divalent linking group represented by R ² include —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S at the terminal of the alkylene group. A heteroatom or a heteroatom selected from-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- It may have a partial structure and be linked to Z via the heteroatom or a partial structure containing a heteroatom.

In general formula (1), Z represents a group having a heterocyclic structure. Examples of the group having a heterocyclic structure include phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, indanthrone series, and flavan. Throne, perinone, perylene, thioindigo dye structures, such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, Heterocycles such as zothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazole, phenothiazine, phenoxazine, benzimidazole, benztriazole, cyclic amide, cyclic urea, cyclic imide Structure is mentioned. These heterocyclic structures may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, an alkoxycarbonyl group, and the like. Can be mentioned.

Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and particularly preferably a group having a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, and cyclic urea structure. And a cyclic imide structure are preferable, and a structure represented by the following (2), (3) or (4) is particularly preferable.

In the general formula (2), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR ^A —, and One selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, X in the general formula (2) is preferably a single bond, a methylene group, —O— or —C (═O) —, particularly preferably —C (═O) —.

In the general formula (4), Y and Z each independently represent —N═, —NH—, —N (R ^B ) —, —S—, or —O—. R ^B represents an alkyl group, and when R ^B represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (4), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Examples of the combination of Y and Z include a combination in which one of Y and Z is —N═ and the other is —NH—, and an imidazolyl group.

In general formulas (2), (3), and (4), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specifically, examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like. Examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring. Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.

Among the structures represented by the general formulas (2), (3) and (4), a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (2) or In (4), a benzene ring is more preferable, and in the general formula (3), a naphthalene ring is more preferable.

In the polymer compound having a heterocyclic ring in the side chain of this embodiment, preferred specific examples of the monomer, maleimide, and maleimide derivative represented by the following general formula (1) are listed below, but the present invention is not limited thereto. Is not to be done.

The polymer compound having a heterocyclic ring in the side chain used in this embodiment contains only one type of copolymer unit derived from the monomer represented by the general formula (1), maleimide, and maleimide derivative. It may also include two or more. In the polymer compound having a heterocyclic ring in the side chain of the present embodiment, the content of the copolymer unit derived from the monomer represented by the general formula (1), maleimide, and maleimide derivative is not particularly limited. When the total structural unit contained in the polymer compound having a heterocyclic ring in the side chain of this embodiment is 100% by mass, it is derived from the monomer represented by the general formula (1), the maleimide, and the maleimide derivative. The copolymer unit is preferably contained in an amount of 5% by mass or more, more preferably 10 to 50% by mass. Among the monomers represented by the general formula (1), maleimide, and maleimide derivatives, the monomer represented by the general formula (1) is preferable because of its high adsorptivity to water-insoluble compounds.

That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of a water-insoluble compound, or to effectively weaken the cohesive force of the secondary aggregates, the general formula (1) The content of the copolymer unit derived from the monomer, maleimide, and maleimide derivative represented is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter with a photocurable composition containing a dispersion composition, the content of copolymer units derived from the monomer represented by the general formula (1) is It is preferable that it is 50 mass% or less.

The polymer compound having a heterocyclic ring in the side chain of this embodiment preferably further contains a copolymer unit derived from a monomer having an acid group. When the polymer compound further contains a copolymer unit derived from a monomer having an acid group, when the dispersion composition of the water-insoluble compound is applied to the photosensitive composition, it is excellent in the development removability of the unexposed area. .
Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) mono (2-methacryloyloxyethyl) mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto It can be mentioned mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate. The polymer compound of this embodiment may include only one type of copolymer unit derived from a monomer having an acid group, or may include two or more types.

In the polymer compound having a heterocyclic ring in the side chain of this embodiment, the content of the copolymer unit derived from the monomer having an acid group is preferably 50 to 200 mgKOH / g, particularly preferably 80 to 200 mgKOH. / G. A more preferred range is 100 to 180 mg KOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of copolymer units derived from the monomer having an acid group is preferably 50 mgKOH / g or more. When the acid value is 200 mgKOH / g or more, aggregation between acid groups becomes strong, aggregation between processed pigments occurs, and dispersibility deteriorates. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of water-insoluble compounds, or to effectively weaken the cohesive force of secondary aggregates, a monomer having an acid group is used. The content of the derived copolymer unit is preferably in the above range.

The polymer compound having a heterocyclic ring in the side chain in the present embodiment may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid, which have been mentioned as the affinity sites with the dispersion medium in the description of the embedding dispersant. Examples thereof include diesters, fumaric acid diesters, itaconic acid diesters, styrenes, and vinyl ethers.

The preferred molecular weight of the polymer compound having a heterocyclic ring in the side chain according to this embodiment is in the range of 1,000 to 100,000 in terms of mass average molecular weight (Mw) and in the range of 400 to 50,000 in terms of number average molecular weight (Mn). A range is preferable. More preferably, the weight average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the mass average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.

That is, from the viewpoint of effectively suppressing the formation of secondary aggregates, which are aggregates of primary particles of water-insoluble compounds, or effectively reducing the cohesive force of secondary aggregates, The mass average molecular weight (Mw) of the polymer compound having a heterocyclic ring in the side chain is preferably 1,000 or more. In addition, from the viewpoint of developability when producing a color filter with a photocurable composition containing a dispersion composition of a water-insoluble compound, the mass average molecular weight of the polymer compound having a heterocyclic ring in the side chain of the present embodiment (Mw) is preferably 100,000 or less.
In the dispersion composition of the water-insoluble compound of the present embodiment, the content of the polymer compound having a heterocyclic ring is, as a mass ratio, the polymer compound having a heterocyclic ring in the water-insoluble compound side chain = 1: 0.01 to 1. : 2 is preferable, more preferably 1: 0.05 to 1: 1, and still more preferably 1: 0.1 to 1: 0.6.

The polymer compound having a heterocyclic ring is, for example, a monomer represented by the general formula (1), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. It can be produced by a radical polymerization method. In general, a suspension polymerization method or a solution polymerization method is used. Solvents used in the synthesis of such polymers include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl. Examples include acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. . These solvents may be used alone or in combination of two or more.

In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

[Polymer Compound B]
In this embodiment, a polymer compound (hereinafter referred to as “specific polymer”) containing at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II): In some cases).

In the general formulas (I) and (II), R ¹ to R ⁶ each independently represents a hydrogen atom or a monovalent organic group, and X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each independently represent a single bond or a divalent organic linking group. , A ¹ and A ² each independently represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents 1 to 100 Represents an integer.

R ¹ to R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group and an alkoxy group (preferably having a carbon number of 1 to 5, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, Examples include 3-hydroxypropyl group, 2-hydroxypropyl group, and 2-methoxyethyl group.
R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency of water-insoluble compounds on the particle surface. preferable.

X ¹ and X ² each independently represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. Among them, —C (═O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of the adsorptivity of water-insoluble compounds to particles, and —C (═O) O— is most preferable.

L ¹ and L ² each independently represents a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms. In addition, examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom, and among them, an oxygen atom and a nitrogen atom are preferable.
Specific examples of preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
When the alkylene group has a substituent, examples of the substituent include a hydroxy group.
The divalent organic linking group includes a heteroatom or a heteroatom selected from —C (═O) —, —OC (═O) —, and —NHC (═O) — at the end of the above alkylene group. A substance having a partial structure and connected to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of the adsorptivity to water-insoluble compound particles. Here, the adjacent oxygen atom means an oxygen atom that is bonded to L ¹ in the general formula (I) and L ² in the general formula (II) on the side chain end side.

A ¹ and A ² each independently represents a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree group Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkyls Rufinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkyl Sulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group) Dialkylphosphono group _{_{(-PO 3 (alkyl) 2)}} , diaryl phosphono group _{_{(-PO 3 (aryl) 2)}} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate) Group), a phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (— OPO ₃ _{(aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} ) , Monoalkyl phosphono group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its Examples thereof include a conjugated base group (hereinafter referred to as arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
Examples of the substituent include alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.

Specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl , Can be exemplified phosphonophenyl phenyl group.

As A ¹ and A ² , from the viewpoint of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. More preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.

M and n each independently represents an integer of 2 to 8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

P and q each independently represents an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.

The specific polymer in this embodiment is preferably a polymer containing a repeating unit represented by the general formula (I) from the viewpoint of dispersion stability.

The repeating unit represented by the general formula (I) is more preferably a repeating unit represented by the following general formula (I) -2.

In the general formula (I) -2, R ¹ to R ³ each independently represent a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents —C (═O) — or —NHC (═O) —, A ¹ represents a monovalent organic group, m represents an integer of 2 to 8, and p represents an integer of 1 to 100 Represents.

The repeating unit represented by the general formula (I), (II), or (I) -2 is a simple unit represented by the following general formula (i), (ii), or (i) -2, respectively. The polymer is introduced as a repeating unit of the polymer compound by polymerization or copolymerization.

In the general formulas (i), (ii), and (i) -2, R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, and X ¹ and X ² are each Independently represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and L ¹ and L ² each independently represent a single bond or 2 A valent organic linking group, La represents an alkylene group having 2 to 10 carbon atoms, Lb represents —C (═O) — or —NHC (═O) —, and A ¹ and A ² represent Each independently represents a monovalent organic group, m and n each independently represents an integer of 2 to 8, and p and q each independently represents an integer of 1 to 100.

Specific preferred examples of the monomer represented by the general formula (i), (ii), or (i) -2 [monomers (A-1) to (A-23)] are listed below. However, the present invention is not limited to these.

The specific polymer in this embodiment should just contain the at least 1 sort (s) of repeating unit selected from the repeating unit represented by either of general formula (I) and (II), and contains only 1 type. There may be two or more kinds.

In the specific polymer, the content of the repeating unit represented by any one of the general formulas (I) and (II) is not particularly limited, but the total repeating unit contained in the polymer is 100% by mass. In this case, the repeating unit represented by any one of the general formulas (I) and (II) is preferably contained in an amount of 5% by mass or more, more preferably 50% by mass, and 50% by mass to 80% by mass. It is more preferable to contain.

The specific polymer in the present embodiment includes a monomer having a functional group capable of being adsorbed, and the aforementioned general formulas (i), (ii), (i)- It is preferably a polymer compound obtained by copolymerizing the monomer represented by 2. Specific examples of the monomer having a functional group that can be adsorbed to water-insoluble compound particles include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and an ion. And monomers having a functional group. Among these, monomers having an organic dye structure or a heterocyclic structure are preferable in terms of adsorption power.

The monomer having an organic dye structure or a heterocyclic structure is selected from the group consisting of the monomer represented by the general formula (1) described in the high part of the polymer compound A, maleimide, and a maleimide derivative. Preferably it is a seed. The preferred range is also as defined above.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

The specific polymer in this embodiment preferably includes a repeating unit derived from a monomer having an acidic group as described above. By including such a repeating unit, when the dispersion of the present invention is applied to a colored photosensitive composition, the development removability of an unexposed portion is excellent.

The specific polymer in this embodiment may include only one type of repeating unit derived from a monomer having an acidic group, or may include two or more types.
In the specific polymer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. In order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of a water-insoluble compound, or to effectively weaken the cohesive force of secondary aggregates, it is derived from a monomer having an acidic group. The content of the repeating unit is preferably 50 mgKOH / g to 200 mgKOH / g.

As the monomer having a basic nitrogen atom, each exemplified compound, urea group, urethane group, and coordinating oxygen atom in the monomer that forms a basic group, which has been mentioned as the functional group in the description of the embedding dispersant previously, Examples of each compound (especially exemplified compounds u-1 to u-12) in monomers having a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group can be given. Furthermore, each example compound in the monomer which has the ionic group illustrated previously similarly is also mentioned.

The monomer having a functional group capable of adsorbing to the particles of the water-insoluble compound can be appropriately selected according to the type of the water-insoluble compound to be dispersed. These may be used alone or in combination of two or more. Also good.

The specific polymer in this embodiment may further contain a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.

Examples of vinyl monomers that can be used here include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid diesters that have been cited as the affinity sites for the dispersion medium in the description of the embedding dispersant. , Fumaric acid diesters, itaconic acid diesters, styrenes, or vinyl ethers.

Preferred embodiments of the specific copolymer in this embodiment include at least a monomer represented by the general formula (i), (ii), or (i) -2, and a monomer having an organic dye structure or a heterocyclic structure. More preferably, at least the monomer represented by the above general formula (i) -2, the monomer represented by the above general formula (11), and an acid group And a monomer having a copolymer.
According to this embodiment, a dispersion composition excellent in adsorption of water-insoluble compounds to particles and excellent in developability can be provided.

The preferred molecular weight of the polymer compound having a heterocyclic ring in the side chain according to this embodiment is a mass average molecular weight (Mw) in the range of 1,000 to 100,000, and a number average molecular weight (Mn) of 400 to 50,000. A range is preferable. More preferably, the weight average molecular weight (Mw) is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 30,000. In particular, the mass average molecular weight (Mw) is most preferably in the range of 8,000 to 30,000, and the number average molecular weight (Mn) is in the range of 4,000 to 12,000.
That is, from the viewpoint of effectively loosening secondary aggregates, which are aggregates of primary particles of water-insoluble compounds, or effectively weakening reaggregation, the mass average molecular weight (Mw) of the specific polymer is It is preferable that it is 1000 or more. Moreover, from the viewpoint of developability when producing a color filter with a colored photosensitive composition containing a dispersion composition, the mass average molecular weight (Mw) of the specific polymer is preferably 30000 or less.

The specific polymer in this embodiment includes, for example, a monomer represented by the following general formula (i), (ii), or (i) -2, and another radical polymerizable compound (described above) as a copolymerization component. Can be produced by a normal radical polymerization method. In general, a suspension polymerization method or a solution polymerization method is used. Solvents used in the synthesis of such a specific polymer include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.

In the dispersion composition of the water-insoluble compound of this embodiment, the content of the specific polymer is preferably a mass ratio of water-insoluble compound: specific polymer = 1: 0.1 to 1: 2, more preferably 1 : 0.2 to 1: 1, more preferably 1: 0.4 to 1: 0.7.

In addition, other polymer compounds may be used at the same time in addition to the above-mentioned specific copolymer as necessary, as long as the effects of the present embodiment are not impaired. As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used. The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins. Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

[Polymer Compound C]
The polymer compound of this embodiment preferably has acrylic acid in the main chain, the acrylic acid content is preferably 5 to 30% by mass, and the graft type has a mass average molecular weight in the range of 1,000 to 100,000. A polymer compound is preferred.

As for the specific graft polymer, an acrylic acid group may be contained in the main chain. Further, an acrylic acid group may be further included in the branch part. As a method for synthesizing a specific graft polymer, as described in New Polymer Experiments Vol. 2 (Kyoritsu Shuppan, 1995), etc., as a general method, (1) a method of polymerizing a branch monomer from a main chain polymer, ( 2) A method of bonding a branched polymer to a main chain polymer (3) A method of copolymerizing a main chain monomer with a branched polymer can be used. That is, the specific graft polymer is preferably obtained by copolymerizing acrylic acid, a polymerizable oligomer (hereinafter referred to as macromonomer) and another copolymerizable monomer.

The amount of acrylic acid introduced is preferably 5 to 30% by mass from the viewpoint of dispersibility. If it exceeds 30% by mass, the amount of macromonomer to be copolymerized becomes relatively small, so that the steric repulsion chain does not contribute and sufficient dispersion stability cannot be obtained. On the other hand, if it is 5% by mass or less, sufficient flexibility cannot be obtained as a whole polymer compound, and it is difficult to obtain the effects of improving dispersion stability and developability. Furthermore, the amount of acrylic acid introduced is preferably 10 to 30% by mass, and most preferably 10 to 25% by mass, although it depends on the type and molecular weight of the macromonomer.

[Polymer Compound D]
The polymer compound of this embodiment preferably has a repeating unit selected from the following general formulas (31) and (32), and more preferably contains 5 to 100% by mass of the repeating unit. A polymer compound having a mass average molecular weight of 1,000 to 100,000 is preferable.

General formula (31)
-Q ¹ -Q ² -Z-
Where Q ¹ represents — (C═O) — or —SO ₂ —,
Q ² represents —NH— or —CHR ¹ —,
Z represents — (C═O) —R ² — or —SO ₂ —R ² —.
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group,
R ² represents an alkylene group, a cycloalkylene group, or an arylene group.
R ¹ and R ² may be linked to each other via a linking group.
Formula (32)
-Rf-OH
Here, Rf represents an alkylene group substituted with at least one fluorine atom.

Specific examples of the partial structure represented by the general formula (31) (hereinafter sometimes referred to as an acid group or an acid group structure) include the following structures.

Examples of the acid group represented by the general formula (32) include —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, —CH (CF ₃ ) OH and the like can be mentioned, and —C (CF ₃ ) ₂ OH is preferable.

The amount of the acid groups of the general formula (31) and the general formula (32) contained in the polymer compound can be appropriately adjusted according to the type of the water-insoluble compound to be dispersed. The amount of the repeating unit containing an acid group is preferably 5 to 100% by mass, preferably 10 to 80% by mass, and more preferably 20 to 60% by mass. The acid value is preferably 30 to 300 mgKOH / g, more preferably 50 to 200 mgKOH / g. When the acid value is less than 30 mgKOH / g, development cannot be performed or a development residue occurs. When the acid value exceeds 300 mgKOH / g, the dispersibility stability becomes poor, or the speed in alkali development becomes too fast, and an appropriate development latitude cannot be obtained.
The acid value is based on the measurement of the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer compound. A polymer compound having a desired acid value can be obtained by adjusting the number of acid groups possessed by the monomer, the molecular weight of the monomer, the composition ratio of the monomers, and the like, and controlling the number of acidic groups possessed by the polymer compound.

Specifically, the polymer compounds may introduce the general formulas (31) and (32) by polymerizing monomers represented by the following general formulas (GI) to (G-III). It is possible and preferable.

In the general formulas (GI) to (G-III), R ³ represents a hydrogen atom or a methyl group. S ¹ represents a linking group represented by the general formulas (1-a) to (1-f). R represents an alkyl group, a cycloalkyl group or an aryl group which may have a substituent. Rf represents an alkylene group substituted with at least one fluorine atom. W ² is a single bond or

(Z ¹ and Z ² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, and a hydroxyl group, and Z ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and the number of carbon atoms. Represents a 6-20 aryl group), or a single linking group selected from an atomic group such as linking group or any combination thereof.

The general formulas (GI) to (G-III) are preferably represented by the following general formulas (G-IV) to (G-VII).

(W ¹ represents a single linking group selected from alkylene, alkoxy and ester, or a linking group composed of any combination. S ¹ is represented by the above general formulas (1-a) to (1-f). R ¹ represents an optionally substituted alkyl group, cycloalkyl group or aryl group, R ² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, An alkoxy group and a cyano group, R ³ represents a hydrogen atom or a methyl group, and Rf represents an alkylene group substituted with at least one fluorine atom.

Specific examples of general formulas (G-III) to (G-VII) are shown below. R ³ represents a hydrogen atom or a methyl group.

The polymer compound of this embodiment can be synthesized by polymerizing monomers as described above, or can be synthesized by reacting a precursor polymer compound with a low molecular compound having an acid group.
The polymer compound of this embodiment is more preferably at least one selected from a block polymer, a graft polymer, and a terminal-modified polymer.

The polymer compound of this embodiment is considered to act to adsorb on the particle surface of the water-insoluble compound and prevent reaggregation in the dispersion step. Therefore, the polymer compound of this embodiment may be a linear random copolymer, but a block polymer, a graft polymer, and a terminal-modified polymer that are more effective can be cited as preferred structures.

(Linear type random copolymer)
A linear random copolymer is obtained by subjecting a monomer containing an acid group represented by the above general formulas (GI) to (G-III) to any other copolymerizable monomer by any polymerization method such as radical polymerization. Obtainable. Other copolymerizable monomers are described in detail in the section of block type polymer. (I) Monomer having organic dye structure or heterocyclic structure, (ii) Monomer having acidic group, (iii) Basic A monomer having a nitrogen atom, (iv) a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group, (v) Monomers containing ionic functional groups, (vi) (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, etc. Monomers optionally may be selected one or more. It is preferable to include at least one selected from the monomer groups (i) to (iii).

The preferred mass average molecular weight of the linear random copolymer is not particularly limited, but is preferably in the range of 1,000 to 100,000, and more preferably in the range of 3,000 to 50,000. When the mass average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the mass average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

(Block type polymer)
Although it does not specifically limit as a block type polymer, The block type polymer which consists of a water-insoluble compound adsorption block (a), the block (b) which has an acid group, and the block (c) which does not adsorb | suck to a water-insoluble compound particle | grain. Is mentioned.
Although it does not restrict | limit especially as a monomer which comprises adsorption block (a), For example, the monomer which has a functional group which can adsorb | suck to the particle | grains of a water-insoluble compound is mentioned. Specific examples include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom.

Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, anthanthrone series, Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolin Emissions, benzimidazolone, benzothiazole, succinimide, may phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, be mentioned a monomer having a heterocyclic structure anthraquinone. More specifically, although not particularly limited, monomers having the following structures can be exemplified.

Examples of the monomer having an acidic group may include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group or a phosphoric acid group. Specifically, each compound mentioned as a monomer which has the acidic group which makes the specific polymer of the said high molecular compound B is mentioned. The acid group can be introduced separately from the acid group described above.

Examples of the monomer having a basic nitrogen atom include vinylpyridine, vinylimidazole, vinyltriazole and the like as the monomer having a heterocyclic ring. In addition to this, as the monomer having a basic nitrogen atom, In the description, each exemplified compound in the monomer that forms a basic group mentioned as the functional group, urea group, urethane group, hydrocarbon group having 4 or more carbon atoms having a coordinating oxygen atom, alkoxysilyl group, epoxy group, isocyanate Specific examples of the monomer having a group or a hydroxyl group (particularly exemplified compounds u-1 to u-12) can be given. Furthermore, each example compound in the monomer which has the ionic group illustrated previously similarly is also mentioned.

Furthermore, the monomer containing the ionic functional group previously mentioned as the functional group in the description of the embedding dispersant can be used.

Examples of the monomer constituting the block (b) having an acid group include those already described. Preferably, it is composed of monomers represented by the above general formulas (GI) to (G-III).
The monomer having an acid group can be appropriately selected according to the type of the water-insoluble compound to be dispersed, and these may be used alone or in combination of two or more.

The monomer constituting the block (c) that is not adsorbed on the water-insoluble compound particles is not particularly limited. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, Examples thereof include fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, and (meth) acrylonitrile. These monomers may be used independently and may use 2 or more types together.

Specifically, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters mentioned above as the affinity sites with the dispersion medium in the description of the embedding dispersant. , Itaconic acid diesters, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinylcaprolactone, etc. Can be mentioned.

As a method for obtaining a block type polymer, a conventionally known method can be used. For example, living polymerization, iniferter method and the like are known, and as another method, thiolcarboxylic acid or 2-acetyl is used in radical polymerization of a monomer having an adsorbing group or a monomer having no adsorbing group. A polymer obtained by polymerizing a compound containing a thioester and a thiol group in a molecule such as thioethyl ether or 10-acetylthiodecanethiol is treated with an alkali such as sodium hydroxide or ammonia, There is also known a method in which a polymer having a thiol group at one end and radical polymerization of the monomer component of the other block in the presence of the obtained polymer having a thiol group at one end. Among these, living polymerization is preferable.

The mass average molecular weight of the block polymer is not particularly limited, but is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the mass average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the mass average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

(Graft type polymer)
The graft polymer may contain the acid group described above in either the main chain or the branch, or both. The method for synthesizing the graft polymer is, as described in New Polymer Experiments Vol. 2 (Kyoritsu Shuppan, 1995), as a general method of polymerizing a branch monomer from a main chain polymer, A method of bonding a branched polymer to a molecule, a method of copolymerizing a main chain monomer with a branched polymer, and the like can be used.

That is, the graft-type polymer that can be used in this embodiment is a monomer containing an acid group represented by the above general formulas (GI) to (G-III) in either the main chain or the branch or both. It is obtained by copolymerizing one or more kinds with other copolymerizable monomers.
Other copolymerizable monomers include the above-mentioned (i) monomers having an organic dye structure or a heterocyclic structure, (ii) monomers having an acidic group, (iii) monomers having a basic nitrogen atom, (iv) urea A group having 4 or more carbon atoms, a urethane group, a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group-containing monomer, (v) a monomer containing an ionic functional group, vi) (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins , Maleimides, (meth) acrylonitrile and other monomers It can be.

As a preferable form in the graft type polymer of this embodiment, the following forms may be mentioned.
-Monomers represented by the aforementioned (i) to (iv), monomers containing acid groups represented by the above general formulas (GI) to (G-III), polymerizable oligomers (hereinafter referred to as macromonomers) Graft-type polymer having a copolymer component.
A monomer represented by the above (i) to (iv) and a polymerizable oligomer (hereinafter referred to as a macromonomer) containing an acid group represented by the general formulas (GI) to (G-III) are combined. Graft type polymer as a polymerization component.
The above-mentioned monomers represented by (i) to (iv), monomers containing acid groups represented by the above general formulas (GI) to (G-III), the above general formulas (GI) to (G A graft-type polymer comprising a polymerizable oligomer (hereinafter referred to as a macromonomer) containing an acid group shown in -III) as a copolymerization component.

The mass average molecular weight of the graft polymer is not particularly limited, but is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the mass average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the mass average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.
In particular, the weight average molecular weight of the branch is preferably 300 to 30,000. More preferably, it is 1,000 to 20,000. When the molecular weight of the branch portion is in the above range, the developability is particularly good and the development latitude is wide.

(Terminal modified polymer)
The terminal-modified polymer is a polymer having a repeating unit having the acid group of this embodiment in the main chain and having a functional group having a high affinity for a water-insoluble compound at the terminal. That is, as the main chain, the above-mentioned linear random copolymer can be used as it is. As the monomer used for copolymerization, for example, as the radical polymerizable monomer, the above-mentioned “monomer having acid group (b)” and “monomer constituting a block that is not adsorbed to water-insoluble compound particles (c ) "Can be used. The terminal-modified polymer that can be used in this embodiment is a polymer obtained by subjecting the terminal of this linear random copolymer to the modification described below.

A method for synthesizing a polymer having a functional group at the end of the polymer is not particularly limited, and examples thereof include the following methods and a combination thereof.
1. 1. A method of synthesizing by polymerization (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.) using a functional group-containing polymerization initiator. Method of synthesizing by radical polymerization using a functional group-containing chain transfer agent The functional groups introduced here are organic dye structures, heterocyclic structures, acidic groups, groups having basic nitrogen atoms, urea groups, urethane groups, coordination groups Examples thereof include groups having a coordinated oxygen atom, hydrocarbon groups having 4 or more carbon atoms, alkoxysilyl groups, epoxy groups, isocyanate groups, hydroxyl groups, and ionic functional groups.

Examples of the chain transfer agent capable of introducing a functional group at the polymer terminal include mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- ( 2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3- Mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol 3-mercapto-2-pig , Mercaptophenol, 2-mercaptoethylamine, 2-mercapruimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Certain disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) can be mentioned.

Examples of the polymerization initiator capable of introducing a functional group into the polymer terminal include 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4,4′- Azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2, 2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide ] Or this Derivatives of al the like.

The molecular weight of the above terminal-modified polymer is preferably a mass average molecular weight of 1,000 to 50,000. When the number average molecular weight is 1,000 or more, a steric repulsion effect as a dispersant for a water-insoluble compound can be obtained more effectively, and when it is 50,000 or less, the steric effect is more effectively suppressed. In addition, the time for adsorption of the water-insoluble compound to the particles can be further shortened.

Although the water-insoluble compound used in the present invention is not particularly limited, specifically, for example, organic pigments, organic dyes, fullerenes, polydiacetylenes, polyimides and other high molecular organic materials, aromatic hydrocarbons or aliphatic hydrocarbons (for example, Particles composed of aromatic hydrocarbons or aliphatic hydrocarbons having orientation, or aromatic hydrocarbons or aliphatic hydrocarbons having sublimability), and organic pigments, organic dyes, or polymeric organic materials are preferred. Organic pigments are particularly preferred. Further, the organic particles may be used singly, or a plurality of organic particles may be combined, or a plurality of water-insoluble compounds may be used to form a multilayer particle structure.

The organic pigment is not limited in hue, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

For more details, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene compound pigments such as C.I. Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105), or C.I. I. Perinone compound pigments such as C.I. Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment Red 207 (C.I. No. 73900, 73906) or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone compound pigment; I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridonequinone compound pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone compound pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone compound pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone compound pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20035), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensed compound pigments such as CI Pigment Brown 23 (C.I. No. 20060); I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo compound pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo compound pigments such as CI Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone compound pigments such as C.I. Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment green 36 (C.I. No. 74265), C.I. I. Pigment green 37 (C.I. No. 74255), C.I. I. Pigment green 58, C.I. I. Pigment blue 16 (C.I. No. 74100), C.I. I. Pigment blue 75 (C.I. No. 74160: 2), C.I. I. Pigment blue 79 (C.I. No. 761300), C.I. I. Pigment Blue 15: 6 (C.I. No. 74160), or C.I. I. Phthalocyanine compound pigments such as C.I. Pigment Blue 15: 3 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800), or C.I. I. Pigment Blue 61 (C.I. No. 42765: 1) and the like triarylcarbonium compound pigments, C.I. I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Pigment Violet 37 (C.I. No. 51345), Pigment Blue 80 and other dioxazine compound pigments, C.I. I. Aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole compound pigments such as C.I. Pigment Orange 73; I. Thioindigo compound pigments such as C.I. Pigment Red 88 (C.I. No. 7313); I. Pigment yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210), an isoindoline compound pigment such as C.I. I. Pigment yellow 109 (C.I. No. 56284), C.I. I. Pigment yellow 185 (C.I. No. 56290), or C.I. I. Pigment Orange 61 (C.I. No. 11295) and the like, an inindolinone compound pigment such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pyranthrone compound pigments such as C.I. Pigment Red 216 (C.I. No. 59710); I. Quinophthalone pigments such as CI Pigment Yellow 138; I. And isoviolanthrone compound pigments such as CI Pigment Violet 31 (60010). Among these, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, or azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments (zinc phthalocyanine, More preferred are aluminum phthalocyanine and the like.

In the fine particles of the present invention or dispersions thereof, two or more water-insoluble compounds or solid solutions thereof can be used in combination, or can be used in combination with ordinary dyes. In the dispersion containing fine particles of the present invention, the content of the water-insoluble compound is preferably 1 to 60% by mass, and more preferably 2 to 50% by mass.

The fine particles obtained in the present invention are desirably water-insoluble compounds that can be stably dispersed in a dispersion medium. Regarding the particle size of fine particles, there is a method of expressing the average size of the population by quantifying by a measurement method, but it is often used that the mode diameter indicating the maximum value of the distribution, the median value of the integral distribution curve There are corresponding median diameters, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle diameter is the number average diameter. Say. The average particle size of the fine particles (primary particles) of the present invention is preferably 100 nm or less, more preferably 75 nm or less, and particularly preferably 50 nm or less. The fine particles of the present invention are single crystals, polycrystals or aggregates of that size, and the fine particles may be crystalline particles, amorphous particles, or a mixture thereof.

The fine particles of the present invention can be described as being embedding a specific dispersant 2 as a disperse phase with the water-insoluble compound 1 as shown in FIGS. However, other components may be incorporated or adhered. At this time, as the embedded dispersing agent 2, there are shown an embedded embedding dispersant 2b in which the whole molecule is encapsulated and an outer embedding dispersing agent 2a in which a part thereof extends outward. The outward extending portion 2o of the external embedding dispersant 2a is continuous with the internal portion 2i, and the outward extending portion 2o has a steric repulsive portion, while the internal portion 2i is insoluble in water. It preferably has a site that exhibits an interaction that attracts the compound. Such molecular structure and its design embodiments are as described above.

In the fine particles of the present invention, as described above, the outer region Ao located at 50% (r ₂ / R) of the particle radius from the particle surface (that is, the center point c in FIG. 1-2). An area outside the segment line k where the radius inner distance r ₁ from the segment line k to the segment outer line k is equal to the radius outer distance r ₂ from the segment line k to the surface predetermined point h (preferably r ₂ / R is 40% More preferably, 80% or more of the dispersant 2 embedded in the region where r ₂ / R is 30%)). In other words, the embedding dispersant 2 in the inner region Ai is less than 20%. In the present invention, measurement and evaluation of surface uneven distribution in which the embedding dispersant is unevenly distributed in the outer region are performed according to the methods described in the following examples unless otherwise specified.

In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the uniformity (monodispersity) of the particles, unless otherwise specified. The monodispersity of the organic nanoparticles (primary particles) of the present invention (in the present invention, monodispersity means the degree of uniform particle size), that is, Mv / Mn is 1.0 to 2.0. It is preferably 1.0 to 1.8, more preferably 1.0 to 1.5.

Examples of the method for measuring the particle size of the organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus using the dynamic light scattering method include Nikkiso's Nanotrac UPA-EX150 and Otsuka Electronics' dynamic light scattering photometer DLS-7000 series (both are trade names).

The fine particles of the water-insoluble compound of the present invention contain (i) the dispersing agent on the good solvent side and / or the poor solvent side when mixing the solution in which the water-insoluble compound is dissolved in the good solvent and the poor solvent. Mixed or (ii) a build-up fine particle that embeds the produced dispersant by preparing a solution in which the dispersant is dissolved in a good solvent separately and mixing with both the solutions preferable.

The amount of the embedding dispersant used is not particularly limited, but the amount added to the system when the fine particles of the water-insoluble compound are precipitated is in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the water-insoluble compound. The range of 10 to 120 parts by mass is more preferable, and the range of 20 to 100 parts by mass is particularly preferable. In the fine particles of the present invention, as described above, it is preferable that 10% by mass or more of the embedding dispersant to be added to the reprecipitation method is embedded. The embedding dispersant may be used alone or in combination of two or more. The content of the embedding dispersant in the dispersion of the present invention is not particularly limited, but the upper limit is an amount added to the above system, and the lower limit is practically an amount embedded in fine particles. Specifically, it is preferably 1 to 294% by mass, more preferably 2 to 99% by mass.

The good solvent is not particularly limited as long as it can dissolve the water-insoluble compound and / or the embedding dispersant, and is compatible with the poor solvent (mixed uniformly). The solubility of the water-insoluble compound in the good solvent is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 50% by mass or less in consideration of a commonly used water-insoluble compound. Further, the solubility of the embedding dispersant in the good solvent is preferably 4.0% by mass or more, and more preferably 10.0% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 70% by mass or less in consideration of a commonly used polymer compound.

The compatibility between the good solvent and the poor solvent is preferably 30% by mass or more, and more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio. When preparing the solution of the water-insoluble compound and the solution of the embedding dispersant separately, it is preferable to select the solution used for dissolving both from water belonging to the range of the good solvent (first solvent). The solvent is preferably the same type of solvent.

The good solvent is not particularly limited, but an organic acid (eg, formic acid, dichloroacetic acid, methanesulfonic acid, etc.), an organic base (eg, diazabicycloundecene (DBU), tetrabutylammonium hydroxide, tetramethylammonium hydroxide). Side, sodium methoxide, etc.), aqueous solvent (eg, water, hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvent (eg, methanol, ethanol, n-propanol, etc.), ketone solvent (eg, methyl ethyl ketone, methyl isobutyl) Ketones, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, Samethylene sulfoxide, sulfolane, etc.), ester solvents (eg, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.) , Aromatic hydrocarbon solvents (eg, toluene, xylene, etc.), aliphatic hydrocarbon solvents (eg, octane, etc.), nitrile solvents (eg, acetonitrile, etc.), halogen solvents (eg, carbon tetrachloride, dichloromethane) Etc.), ionic liquids (for example, 1-ethyl-3-methylimidazolium tetrafluoroborate, etc.), carbon disulfide solvents, or mixtures thereof.

Among these, an organic acid, an organic base, an aqueous solvent, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, an amide solvent, or a mixture thereof is more preferable, and an organic acid, an organic base , Sulfoxide solvents, amide solvents, or mixtures thereof are particularly preferred.

Specific examples include compounds described in paragraphs [0076] to [0087] of JP-A-2009-79158, and preferred ranges are also the same.

There are no particular restrictions on the conditions for preparing the water-insoluble compound solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

When water-insoluble compounds are uniformly dissolved in a good solvent, in general, in the case of pigments having an alkaline dissociable group in the molecule, there is no alkali, but there is no alkaline dissociable group, and nitrogen is easily added with protons. When there are many atoms in the molecule, it is preferable to use acidity. For example, quinacridone, diketopyrrolopyrrole, disazo condensation compound pigments and halogenated phthalocyanine compounds are alkaline, and phthalocyanine compound pigments are acidic.

In addition to the organic base, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide can also be used as the base used when dissolving with alkali. The amount of the base used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents relative to the water-insoluble compound. Particularly preferred is 0.0 to 20 molar equivalents. In the case of an organic base, the amount is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the water-insoluble compound.

In addition to the organic acids, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid can be used as the acid used when dissolving in an acidic state. The amount of the acid to be used is not particularly limited, but it is often used in an excessive amount compared to the base, and is preferably 3 to 500 molar equivalents relative to the water-insoluble compound, more preferably 10 to 500 molar equivalents. It is preferably 30 to 200 molar equivalents.

When an inorganic base or an inorganic acid is mixed with an organic solvent and used as a good solvent for a water-insoluble compound, the alkali or acid is completely dissolved, so that it has a high solubility in some water or lower alcohol or other alkali or acid. A solvent with can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the water-insoluble compound solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol and the like can be used.

The viscosity of the water-insoluble compound solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

The water-insoluble compound solution is not particularly limited as long as it dissolves a water-insoluble compound and, if necessary, a polymer compound in a good solvent, and may contain other components.
Although it does not specifically limit as another component, The organic compound which has an acidic group, the organic compound which has basicity etc. are mentioned suitably. These components have the action of adsorbing quickly to the deposited pigment when the pigment is precipitated by mixing the water-insoluble compound solution and the poor solvent, and treating the pigment surface to be acidic or basic. Is. The solubility of the other components in the poor solvent is not particularly limited.

Examples of the acidic group of the organic compound having an acidic group that can be used in the present invention include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a phosphonic acid group, a hydroxyl group, and a sulfide group. Is not to be done. Moreover, 1 type may be individual in a molecule | numerator, or 2 or more types may contain the same or different functional group. These organic compounds having an acidic group may be used alone or in combination of two or more. Among these, those having a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are preferable.

Specific examples include compounds described in paragraphs [0063] to [0067] of JP-A-2009-79158.

In the present invention, the addition amount of the organic compound having an acidic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass with respect to the water-insoluble compound. The range of 0.05 to 15% by mass is particularly preferable.

Organic compounds having a basic group include alkylamines, arylamines, aralkylamines, pyrazole derivatives, imidazole derivatives, triazole derivatives, tetrazole derivatives, oxazole derivatives, thiazole derivatives, pyridine derivatives, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, triazines. Derivatives and the like can be mentioned, and alkylamine, arylamine and imidazole derivatives are preferable.

As carbon number of the organic compound which has the said basic group, 6 or more are preferable, More preferably, it is 8 or more, More preferably, it is 10 or more.
Specific examples of the organic compound having a basic group include compounds described in paragraphs [0054] to [0056] of JP-A-2009-79158, and preferred ranges thereof are also the same.

The organic compound having a basic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, based on the water-insoluble compound. It is particularly preferably in the range of ˜15% by mass.

It is also preferable to add an organic compound composed of a basic group and a heterocyclic group.
Examples of such an organic compound include compounds described in paragraphs [0060] to [0087] of JP-A-2009-79158, and preferred ranges thereof are also the same.

The addition amount of the organic compound composed of the basic group and the heterocyclic group is preferably in the range of 0.01 to 30% by mass, and in the range of 0.05 to 20% by mass with respect to the water-insoluble compound. More preferably, it is in the range of 0.05 to 15% by mass.

In addition to the above, pigment derivatives described in JP-A No. 2007-9096 and JP-A No. 7-331182 can be exemplified. The pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor. Refers to a pigment derivative type compound. Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names), and the like. When a pigment derivative is used, the amount used is preferably in the range of 0.5 to 30% by weight, more preferably in the range of 3 to 20% by weight, and more preferably in the range of 5 to 15% by weight with respect to the pigment. It is especially preferable that it is in the range.

The poor solvent is not particularly limited, but the solubility of the water-insoluble compound in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the water-insoluble compound in the poor solvent, 0.0001% by mass or more is practical in consideration of a commonly used water-insoluble compound. The solubility of the self-dispersing polymer compound in the poor solvent is 2.0% by mass or less (insoluble), and preferably 1.0% by mass or less. Although there is no particular lower limit to the solubility of the water-insoluble compound in the poor solvent, 0.001% by mass or more is practical in consideration of a commonly used polymer compound.

The poor solvent is not particularly limited, but an aqueous solvent (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), an alcohol solvent (for example, methanol, ethanol, n-propanol, etc.), a ketone solvent (for example, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents ( For example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (eg, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents (eg, Toluene, xylene, etc.), aliphatic hydrocarbon solvents (eg, octane, etc.), nitrile solvents (eg, acetonitrile, etc.), halogen solvents (eg, carbon tetrachloride, dichloromethane, etc.), ionic liquids (eg, 1-ethyl-3
-Methylimidazolium tetrafluoroborate, etc.), carbon disulfide solvent, or a mixture thereof.
Among these, an aqueous solvent, an alcohol solvent, a ketone solvent, a sulfoxide solvent, an ester solvent, an amide solvent, a nitrile solvent, or a mixture thereof is more preferable, and an aqueous medium, an alcohol solvent, or a mixture thereof. Is particularly preferred.

The aqueous medium refers to water alone or water and water-soluble organic solvent or inorganic salt solution, for example, water, hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like.

Although there are things common between those listed as specific examples of good solvents and those listed as poor solvents, the same thing as a good solvent and a poor solvent is not combined, and each water-insoluble compound and polymer compound employed are Therefore, the solubility in the good solvent should be sufficiently higher than the solubility in the poor solvent. For the water-insoluble compound, for example, the solubility difference is preferably 0.2% by mass or more, and 0.5% by mass or more. It is more preferable. There is no particular upper limit on the difference in solubility between the good solvent and the poor solvent, but it is practical that it is 50% by mass or less in consideration of a commonly used water-insoluble compound. For the polymer compound, for example, the solubility difference is preferably 2.0% by mass or more, and more preferably 5.0% by mass or more. Although there is no particular upper limit to the difference in solubility between the good solvent and the poor solvent, it is practical that the difference is 70% by mass or less in consideration of a commonly used polymer compound.

The state of the poor solvent is not particularly limited, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C. The viscosity of the water-insoluble compound solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

When mixing the water-insoluble compound solution and the poor solvent, either of them may be added and mixed. However, it is preferable to jet the water-insoluble compound solution into the poor solvent and mix the poor solvent. A stirred state is preferred. The stirring speed is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. The rate at which the liquid is supplied from the supply pipe is preferably 1 to 10,000 ml / min, more preferably 5 to 5000 ml / min.

By adjusting the Reynolds number when mixing the water-insoluble compound solution and the poor solvent, it is possible to control the particle diameter of the pigment nanoparticles that are formed by precipitation. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Equation (1), Re represents the Reynolds number, ρ represents the density [kg / m ³ ] of the water-insoluble compound solution, and U represents the relative velocity [m / s when the water-insoluble compound solution and the poor solvent meet. L represents the equivalent diameter [m] of the flow path or supply port where the water-insoluble compound solution meets the poor solvent, and μ represents the viscosity coefficient [Pa · s] of the water-insoluble compound solution.

The equivalent diameter L refers to the diameter of the equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to the flow path. The equivalent diameter L is expressed by the following equation (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Formula (2)
It is preferable to form particles by injecting a water-insoluble compound solution into a poor solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

The relative speed U when the water-insoluble compound solution and the poor solvent meet is defined by the relative speed in the direction perpendicular to the surface of the part where both meet. That is, for example, when a water-insoluble compound solution is injected and mixed in a stationary poor solvent, the speed of injection from the supply port becomes equal to the relative speed U. The value of the relative speed U is not particularly limited, but is preferably 0.5 to 100 m / s, and more preferably 1.0 to 50 m / s.

The density ρ of the water-insoluble compound solution is a value determined by the type of material selected, but is practically, for example, 0.8 to 2.0 kg / m ³ . Further, the viscosity coefficient μ of the water-insoluble compound solution is also a value determined by the material used, the ambient temperature, etc., but the preferred range is synonymous with the preferred viscosity of the water-insoluble compound solution described above.

The smaller the Reynolds number (Re) value, the easier it is to form laminar flow, and the larger the value, the easier it is to form turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.

The mixing ratio of the water-insoluble compound solution and the poor solvent is preferably 1/50 to 2/3 in volume ratio, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8. The particle concentration in the liquid when organic fine particles are precipitated is not particularly limited, but the organic particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg, particularly with respect to 1000 ml of the solvent. The range is preferably 50 to 25000 mg. Further, the preparation scale for generating fine particles is not particularly limited, but the preparation amount of the poor solvent is preferably 10 to 2000 L, more preferably 50 to 1000 L.

In preparing a dispersion by precipitating water-insoluble compound fine particles, at least one poor solvent becomes a good solvent (solubility in the poor solvent is 4.0% by mass or more) in at least one of the water-insoluble compound solution and the poor solvent. A compound (hereinafter sometimes referred to as a particle size adjusting agent) may be contained.

Examples of the polymer particle size adjusting agent include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-part. Butyral product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylic acid, sodium polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, a diallylamine monomer / SO ₂ copolymers, diallylamine hydrochloride / Ma Examples thereof include oleic acid copolymer, polydiallylmethylamine hydrochloride, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymer, condensed naphthalene sulfonate, cellulose derivative, starch derivative and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tongant gum, lignin sulfonate, etc. can be used. Of these, polyvinylpyrrolidone, polyacrylic acid, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, diallylamine monomer / SO ₂ copolymer, and the like are preferable. These particle size adjusting agents can be used singly or in combination of two or more.
The mass average molecular weight is preferably from 1,000 to 500,000, more preferably from 10,000 to 500,000, and particularly preferably from 10,000 to 100,000.

As an anionic particle size adjusting agent (anionic surfactant), N-acyl-N-alkyl taurine salt, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl Examples thereof include phosphoric acid ester salts, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts and the like. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyl taurine salts, those described in JP-A-3-273067 are preferable. These anionic particle size regulators can be used alone or in combination of two or more.

Cationic particle size modifiers (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines derived from aliphatic amines and fatty alcohols, and Examples include salts of cationic substances of imidazoline derived from polyamines and fatty acids. These cationic particle size regulators can be used alone or in combination of two or more.

The amphoteric particle size regulator is a particle size in which the anionic particle size regulator has both an anion group moiety in the molecule and a cationic group moiety in the molecule of the cationic particle size modifier. It is a regulator.

Nonionic particle size adjusting agents (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include alkylamines and glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic particle size regulators may be used alone or in combination of two or more.

The content of the particle size adjusting agent is preferably in the range of 0.1 to 100% by mass with respect to the pigment, more preferably 0.1% in order to further improve the particle size control of the water-insoluble compound fine particles. It is in the range of ˜50 mass%, more preferably in the range of 0.1 to 20 mass%. In addition, the particle size adjusting agents may be used alone or in combination.

The type of the third solvent used by switching from the good solvent (first solvent) and the poor solvent (second solvent) is not particularly limited, but is preferably an organic solvent, such as an ester compound solvent, an alcohol compound solvent, Aromatic compound solvents and aliphatic compound solvents are preferred, ester compound solvents, aromatic compound solvents and aliphatic compound solvents are more preferred, and ester compound solvents are particularly preferred. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents.
In the present invention, not only the above-mentioned third solvent but also a fourth solvent described later, a solvent different from both the good solvent and the poor solvent, which is a medium of the dispersion composition, is collectively referred to as “first solvent”. 3 solvent ".

Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include methanol, ethanol, n-butanol, isobutanol and the like. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-hexane and cyclohexane.

Of these, ethyl lactate, ethyl acetate, ethanol, and 2- (1-methoxy) propyl acetate are preferable, and ethyl lactate and 2- (1-methoxy) propyl acetate are more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the good solvent or the poor solvent.

The timing of adding the third solvent is not particularly limited as long as it is after the precipitation of the water-insoluble compound fine particles, but it may be added to the mixed liquid in which the fine particles are precipitated, or a part of the solvent in the mixed liquid may be removed. It may be added after the removal, or all may be added after removing (concentrating) in advance.
That is, the third solvent can be used as a substitution solvent, and the solvent component consisting of the good solvent and the poor solvent in the dispersion liquid in which the fine particles are precipitated can be substituted with the third solvent.
Alternatively, the third solvent can be added after the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder.

In addition, when the pigment dispersion composition described later is used, after the first solvent removal step (first removal), the third solvent is added to replace the solvent, and the second solvent removal step ( The solvent may be removed and powdered by the second removal). Thereafter, a pigment dispersant and / or a solvent can be added to obtain a desired pigment dispersion composition.
Alternatively, the good solvent and the poor solvent are completely removed (concentrated) and taken out as pigment particle powder, and then the third solvent and / or the pigment dispersant can be added to obtain a desired pigment dispersion composition.
The amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the water-insoluble compound fine particles.

The process for removing the solvent component from the mixed solution after the precipitation of the water-insoluble compound fine particles is not particularly limited, and examples thereof include a method of filtering with a filter and the like, a method of precipitating and concentrating the water-insoluble compound fine particles by centrifugation. It is done.
As an apparatus for filter filtration, for example, an apparatus such as reduced pressure or pressure filtration can be used. Examples of preferable filters include filter paper, nanofilters, and ultrafilters.
Any device may be used as the centrifuge as long as the water-insoluble compound fine particles can be precipitated. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be mentioned. Centrifugation conditions are preferably 50 to 10,000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravity acceleration is applied). The temperature at the time of centrifugation depends on the solvent type of the dispersion, but is preferably −10 to 80 ° C., more preferably −5 to 70 ° C., and particularly preferably 0 to 60 ° C.
In addition, as the solvent removal step, a method of concentrating the solvent by sublimation by vacuum freeze-drying, a method of drying and concentrating the solvent by heating or decompression, a method combining them, or the like can also be used.

The fine particles of the water-insoluble compound can be used in a state dispersed in a vehicle, for example. The vehicle refers to a part of a medium in which a water-insoluble compound is dispersed in a liquid state when it is a paint, and is a part that is liquid and binds to the water-insoluble compound to harden a coating film (binder). And a component (organic solvent) for dissolving and diluting it. In the present invention, the polymer compound used for forming the fine particles and / or the water-insoluble compound dispersant used for redispersion are collectively referred to as a binder.

The concentration of fine particles in the dispersion composition of fine particles after redispersion is appropriately determined according to the purpose, but preferably the fine particles are 2 to 30% by mass, and preferably 4 to 20% by mass with respect to the total amount of the dispersion composition. More preferred is 5 to 15% by mass. When dispersed in the vehicle as described above, the amount of the binder and the dissolved diluent component is appropriately determined depending on the type of the water-insoluble compound and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. It is preferably 3 to 20% by mass, more preferably 5 to 15% by mass. The dissolved and diluted component is preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.

When the fine particles of the water-insoluble compound of the present invention are redispersed in the third solvent, the aggregation state of the water-insoluble compound fine particles is spontaneously solved in the third solvent without adding another dispersant or the like. It preferably has a property of being dispersed in a medium, and this property is referred to as “self-dispersible” or “self-dispersible”. However, in order to further improve the redispersibility in the present invention, a pigment dispersant or the like may be added during redispersion of the fine particles.

As a method of redispersing the fine particles in such an aggregated state, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs. Therefore, the liquid temperature is preferably 1 to 100 ° C., more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
There are no particular restrictions on the disperser used when dispersing the pigment nanoparticles by applying physical energy, for example, dispersers such as kneaders, roll mills, atriders, super mills, dissolvers, homomixers, and sand mills. Can be mentioned. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants can be added to the pigment dispersion composition as long as the effects of the present invention are not impaired.
Examples of pigment dispersants include polymer dispersants (for example, linear polymers, block polymers, graft polymers, terminal-modified polymers, etc.), surfactants (polyoxyethylene alkyl phosphate ester, poly Oxyethylene alkylamine, alkanolamine, etc.), pigment derivatives and the like. The dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
Examples of the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like. Examples of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like. Examples of the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).

In the present invention, the pigment derivative (hereinafter also referred to as “pigment derivative type dispersant”) is derived from an organic pigment as a parent substance, and is manufactured by chemically modifying the parent structure, or It is defined as a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. Generally, it is also called a synergist type dispersant.

Although not particularly limited, for example, a functional group such as a pigment derivative having an acidic group, a pigment derivative having a basic group, or a phthalimidomethyl group described in JP-A-2007-9096, JP-A-7-331182, or the like. The introduced pigment derivative is preferably used.

Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative) and 6750 (azo pigment derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative) and 22000 (azo pigment derivative)” manufactured by Lubrizol (any) Also product name).
Examples of the linear polymer include an alkali-soluble resin described later, and it is also preferable to use the linear polymer in combination with the pigment derivative.
Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.

The photocurable composition contains a dispersion composition of fine particles of the water-insoluble compound, a photopolymerizable compound, and a photopolymerization initiator (hereinafter sometimes referred to as a photopolymerization initiator system), preferably, Furthermore, an alkali-soluble resin is included. Hereinafter, each component of the photocurable composition will be described.

The water-insoluble compound fine particles and the method for producing the dispersion composition have already been described in detail. The content of the fine particles in the photocurable composition is preferably 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content means the total composition excluding the organic solvent), and 20 More preferably, it is ˜80% by mass, and further preferably 25-60% by mass. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

The photopolymerizable compound (hereinafter sometimes referred to as a polymerizable monomer or a polymerizable oligomer) is a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Is preferred. Examples of such a photopolymerizable compound include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned. Further, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490; polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and methacrylates.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

The photopolymerizable compound may be used alone or in combination of two or more. The content of the photocurable composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds), U.S. Pat. No. 2,367,660 Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon substituted fragrances described in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones, Benzothiazole compounds described in Japanese Patent No. 51-48516 and trihalomethyl-s-triazis Compounds, trihalomethyl are described in U.S. Patent No. 4239850 - triazine compounds include U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are preferable.

In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt, and the like may be mentioned as suitable ones. it can.

The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced. The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photocurable composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

The alkali-soluble resin can be added at the time of preparing a photocurable composition or an ink-jet ink for a color filter, but it is also preferably added at the time of producing the fine particle dispersion composition or at the time of forming fine particles. It is also possible to add the alkali-soluble resin to both or one of the poor solvents for adding the water-insoluble compound solution and the water-insoluble compound solution to form fine particles of the water-insoluble compound. Alternatively, it is also preferable to add an alkali-soluble resin solution when forming fine particles of a water-insoluble compound in a separate system.

As the alkali-soluble resin, a binder having an acidic group is preferable, and an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

The alkali-soluble resin may be used alone or in the form of a composition used in combination with a normal film-forming polymer. The amount of water-insoluble compound added to 100 parts by mass of the fine particles is 10 to 200 masses. Parts are common, with 25 to 100 parts by weight being preferred.

In addition, in order to improve the crosslinking efficiency, the side chain of the alkali-soluble resin may have a polymerizable group, and a UV curable resin or a thermosetting resin is also useful. Furthermore, as the alkali-soluble resin, a resin having a water-soluble atomic group in a part of the side chain can be used.

In the photocurable composition, an organic solvent (fourth solvent) for preparing the photocurable composition may be used in addition to the above components. Examples of the fourth solvent include, but are not limited to, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbons. Preferable examples include a system solvent, a nitrile solvent, or a mixture thereof. Among them, a ketone solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or these More preferably, a mixture of
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane.
These solvents may be used alone or in combination of two or more. A solvent having a boiling point of 180 ° C. to 250 ° C. can be used if necessary. The content of the organic solvent is preferably 10 to 95% by mass with respect to the total amount of the photocurable composition.

In addition, it is preferable that an appropriate surfactant is contained in the photocurable composition. Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600. As for content of surfactant, 5 mass% or less is preferable with respect to photocurable composition whole quantity.

The photocurable composition preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl) -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less with respect to the total amount of the photocurable composition.

In addition to the colorant (pigment), a colorant (dye or pigment) can be added to the photocurable composition as necessary. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the photocurable composition. Specific examples of the dyes or pigments include the coloring materials described in JP-A-2005-17716 [0038]-[0040] and JP-A-2005-361447 [0068]-[0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The auxiliary dye or pigment content is preferably 5% by mass or less based on the total amount of the photocurable composition.

The photocurable composition can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series and the like in addition to the compounds described in JP-A-5-72724. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the photocurable composition whole quantity.

In addition, the photocurable composition may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like in addition to the above-described additives.

The photocurable composition can be made into an inkjet ink by adjusting the composition appropriately. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing, but among them, the inkjet ink for the color filter is preferable.
The ink-jet ink is not particularly limited as long as it contains the above-mentioned water-insoluble compound fine particles, and preferably contains the above-mentioned water-insoluble compound fine particles in a medium containing a polymerizable monomer and / or a polymerizable oligomer. Here, as the polymerizable monomer and / or polymerizable oligomer, those described above for the photocurable composition can be used.
At this time, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
Further, the surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20 to 35 mN / m, and most preferably 25 to 30 mN / m. The surface tension can be adjusted by the addition of a surfactant and the type of solvent. For example, the surface tension is obtained by using a measuring device such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

An ordinary ink jet head (hereinafter also simply referred to as a head) can be applied, and a continuous type or a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The drive frequency is preferably 1 to 500 kHz.

In addition, after each pixel is formed, a heating step of performing heat treatment (so-called baking treatment) can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The heating temperature and time depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to obtain sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix stripe shape, a lattice shape, or a delta arrangement. May be.

It is preferable to prepare a partition wall in advance before the pixel forming step using the color filter inkjet ink described above, and to apply ink to a portion surrounded by the partition wall. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.

The components contained in the coating film using the photocurable composition are the same as those already described. Further, the thickness of the coating film using the photocurable composition can be appropriately determined depending on the application, but is preferably 0.5 to 5.0 μm, and preferably 1.0 to 3.0 μm. Is more preferable. In the coating film using this photocurable composition, the above-mentioned monomer or oligomer can be polymerized to form a polymerized film of the photocurable composition, and a color filter having the polymerized film can be produced (about production of a color filter) Will be described later.) Polymerization of the photopolymerizable compound can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

In addition, although the said coating film can be formed by apply | coating and drying a photocurable composition with a normal coating method, in this invention, it is a slit which has a slit-shaped hole in the part which discharges a liquid. It is preferable to apply by a nozzle. Specifically, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

As a method for applying the photocurable composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly applied with high accuracy, and it can be widely used for producing a color filter. However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

For slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate. On the other hand, this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using the slit-shaped nozzle already demonstrated. Preferred specific examples of the slit coater are the same as described above.

The color filter using the fine particles or dispersion thereof of the present invention is preferably excellent in contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.)
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, which is a very important performance in order to replace the liquid crystal display with a CRT.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. In the following examples, “part” and “%” are based on mass unless otherwise specified.

A. Examples and Comparative Examples According to First Embodiment <Preparation of Pigment Dispersion>
[Synthesis Example 1A]
(Synthesis of monomer MM-1)
45.28 parts of 2-thiobarbituric acid and 13.82 parts of sodium hydroxide are dissolved in 200 parts of dimethyl sulfoxide and heated to 25 ° C. To this, 57.53 parts of chloromethylstyrene is dropped, and the mixture is further heated and stirred at 55 ° C. for 5 hours. After heating and stirring, 150 parts of methanol and 150 parts of distilled water are added to the reaction solution and stirred for 1 hour. Subsequently, this solution is poured into 2000 parts of distilled water while stirring, and the resulting precipitate is filtered and washed. As a result, 80.1 parts of monomer MM-1 was obtained.
(Synthesis of polymer PA-1)
The following monomer solution is introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). To do. Then, the following initiator solution is added to said liquid, and it heat-stirs at 78 degreeC for 2 hours. The following initiator solution is further added after heating and stirring, and the operation of heating and stirring at 78 ° C. for 2 hours is repeated twice in total. After the last 2 hours of stirring, the mixture is subsequently heated and stirred at 90 degrees for 2 hours. The obtained reaction solution was poured into 1500 parts of isopropanol while stirring, and the resulting precipitate was collected by filtration and dried by heating to obtain graft polymer PA-1.

(Monomer solution)
・ Monomer MM-1 4.0 parts ・ Styrene 15.0 parts ・ Methacrylic acid 2.0 parts ・ 1-Methyl-2-pyrrolidone 46.67 parts

(Initiator solution)
・ 2.2'-azobis (isobutyrate) dimethyl (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 0.8 part ・ 1-methyl-2-pyrrolidone 2 parts

(Synthesis Examples 2A to 9A)
Polymers PA-2 to PA-9, PA-c1, and PA-c2 were obtained in the same manner as in Synthesis Example 1A, except that the monomer composition and initiator composition shown in Synthesis Example 1A were changed to Table 1A.

(Synthesis Example 10A)
(Synthesis of polymer compound B PA-10)
Into a 500 mL three-necked flask, 160.0 g of ε-caprolactone and 18.3 g of 2-ethyl-1-hexanol were introduced and dissolved with stirring while blowing nitrogen. Monobutyltin oxide 0.1g was added and it heated at 100 degreeC. After 8 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by gas chromatography. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 22.2 g of 2-methacryloyloxyethyl isocyanate was added. After 5 hours, the disappearance of the raw material was confirmed by H NMR, and then cooled to room temperature to obtain 200 g of a solid monomer (A-5). The monomer (A-5) was confirmed by H NMR, IR and mass spectrometry.
The obtained monomer (A-5) is mentioned as a preferred specific example of the monomer represented by the general formula (i), (ii), or (i) -2.

Monomer (A-5) 37.5 g, monomer M-11 5.0 g, methacrylic acid 7.5 g, dodecyl mercaptan 1.3 and 16.7-methoxy-2-propanol 116.7 g were purged with nitrogen. The mixture was introduced into a three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 75 ° C. while flowing nitrogen into the flask. To this was added 0.3 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred with heating at 75 ° C. for 2 hours. Two hours later, 0.3 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of the polymer compound was obtained.
The mass average molecular weight of the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance under the following conditions, and was 18,000. The following table shows the monomers used when synthesizing the polymer compound and the amount charged, the mass average molecular weight of the synthesized polymer, and the acid value.
<Molecular weight measurement conditions>
Equipment: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI detector)
Pre-column: TSKGUARDCOLUMN MP (XL)
6mm x 40mm (manufactured by Tosoh Corporation)
Sample side column: The following two columns are directly connected (all manufactured by Tosoh Corporation)
・ TSK-GEL Multipore-HXL-M 7.8mm × 300mm
Reference side column: Same as sample side column Temperature chamber temperature: 40 ° C
Moving bed: Tetrahydrofuran
Sample-side moving bed flow rate: 1.0 mL / min Reference-side moving bed flow rate: 0.3 mL / min Sample concentration: 0.1% by weight
Sample injection volume: 100 μL
Data collection time: 16 to 46 minutes after sample injection Sampling pitch: 300 msec

(Synthesis Example 11A)
(Synthesis of polymer compound C PA-11)
A three-necked flask in which 14.0 g of M-11, 105.0 g of A-3 synthesized in the same manner as in the above A-5, 21.0 g of acrylic acid, 3.1 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol were substituted with nitrogen The mixture is stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C. To this was added 1.2 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.2 g of V-601 was further added, and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and stirred for 2 hours to obtain a 30% solution of polymer 2.
It was 23,000 as a result of measuring the weight average molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. From the titration with sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

[Table P] Figures in parentheses are mass%.

AA: Acrylic acid MAA: Methacrylic acid

(Synthesis Example 12A)
(PA-12)
The polymer dispersant C-18 (see the following chemical formula) used in Example 2-5 of JP-A-2007-262378 was synthesized and used as PA-12.

(Example AI, Comparative Example AI)
[Example A-1]
To 1000 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries), pigment C.I. I. 50 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) is dispersed, and 52.3 g of a tetramethylammonium hydroxide 25% methanol solution is added dropwise to prepare a pigment solution. did. 30.0 g of graft polymer PA-1 was dissolved in 90 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), and 17.8 g of a tetramethylammonium hydroxide 25% methanol solution was added dropwise to prepare polymer solution 01. did. The pigment solution and the polymer solution 01 were mixed to prepare a pigment / polymer solution 01. As a result of measuring the clay of this pigment / polymer solution 01 using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment polymer solution 01 is 24.5 ° C. Was 14.3 mPa · s. Separately, 1000 ml of ion-exchanged water containing 19 g of 1 mol / l hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.
Here, the pigment / polymer solution 01 was added to 1000 ml of deionized hydrochloric acid-containing ion-exchanged water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.) under temperature control at 5 ° C. The organic pigment was injected at a flow rate of 400 ml / min using a NP-KX-500 large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) at a flow rate of 400 ml / min. Particles were formed to prepare pigment nanoparticle dispersion liquid 01.
The pigment nanoparticle dispersion liquid 01 prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type ro cloth manufactured by Shikishima Canvas Co., Ltd. The obtained pigment nanoparticle concentrated paste 01 was recovered.

The pigment nanoparticle concentrated paste 01 was dried in an oven at 100 ° C. for 8 hours to obtain an organic pigment powder 01 (solid content concentration: 96 mass%) (organic pigment content: 59 mass%).
Using the organic pigment powder 01, a pigment dispersion composition having the following composition was prepared.
Organic pigment powder 01 14.0 g
46.3 g of propylene glycol monomethyl ether acetate
The pigment dispersion composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm to obtain a pigment dispersion composition 01. It was.

[Examples A-2 to A-9]
In the pigment dispersion composition of Example A-1, pigment dispersion compositions 02 to 09 were prepared in the same manner as in Example A-1, except that the graft polymers were PA-2 to PA-9.

[Examples A-10 to A-12]
In the pigment dispersion composition of Example A-1, the amount of graft polymer PA-1 added was reduced from 30.0 g to 10.0 g, and the organic pigment powder was redispersed in propylene glycol monomethyl ether acetate. Pigment dispersion compositions 10 to 12 were prepared in the same manner as in Example A-1, except that 20.0 g of the combined PA-10 to 12 was added.

[Comparative Example A-1]
Sodium chloride and pigment C.I. in 1,3 butylene glycol diacetate solution. I. Pigment Red 254 (trade name: Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 10 g of powder and 6.0 g of graft polymer P-1 were charged into a double-arm kneader and kneaded at 80 ° C. for 15 hours. After kneading, the mixture was taken out into 700 parts by mass of a 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized. Then, 2.4 g of propylene glycol monomethyl ether acetate was added to 1 g of the pulverized product and mixed. The pigment composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm to obtain a pigment dispersion composition c1.

[Comparative Example A-2]
In the pigment dispersion composition of Example 1, pigment dispersion composition c2 was prepared in the same manner as in Example A-1, except that the graft polymer was PA-c1.

[Comparative Example A-3]
To 1000 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries), pigment C.I. I. 50 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 30.0 g of PA-c2 are dispersed in this solution. 3 g was added dropwise to prepare a pigment solution. Separately, 1000 ml of ion-exchanged water was prepared as a poor solvent.
Here, the temperature of the solution was controlled at 5 ° C., and the above-mentioned pigment solution was added to 1000 ml of ion-exchanged water containing hydrochloric acid as a poor solvent stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Using a KX-500 type large capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.), by injecting 100 ml at a flow rate of 400 ml / min from a liquid feed pipe having a flow path diameter of 1.1 mm, And pigment nanoparticle dispersion c3 was prepared. Subsequently, 5% sulfuric acid aqueous solution was dropped into the pigment nanoparticle dispersion c3 to adjust the pH to 4.0, thereby preparing a pigment nanoparticle aggregate.
The pigment nanoparticle aggregated liquid prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. The pigment nanoparticle concentrated paste was recovered.
The pigment nanoparticle concentrated paste was dried in an oven at 100 ° C. for 8 hours to obtain an organic pigment powder c3 (solid content concentration 94 mass%) (organic pigment content 58 mass%).

Using the organic pigment powder c3, a pigment dispersion composition c3 having the following composition was prepared.
14.0 g of the organic pigment powder c3
46.3 g of propylene glycol monomethyl ether acetate
The pigment dispersion composition c3 having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. Obtained.

[Comparative Example A-4]
In the pigment dispersion composition of Example A-1, pigment dispersion composition c4 was prepared in the same manner as in Example 1 except that the graft polymer was polystyrene.

[Comparative Example A-5]
In the pigment dispersion composition of Example A-1, pigment dispersion composition c5 was prepared in the same manner as in Example A-1, except that the graft polymer was polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.). Adjusted.

(Embedded evaluation)
It was confirmed whether the dispersant was embedded in the particles using solid ¹³ C CP / MAS NMR measurement (AVANCE DSX-300 spectrometer manufactured by Bruker BioSpin Co., Ltd. and 4 mmΦ HFX CP / MAS probe). . The solid ¹³ C CP / MAS NMR measurement was performed as follows.
The pigment dispersion composition is subjected to suction filtration using a membrane filter (MILLIPORE cut size: 0.05 μm) to prepare a concentrated paste. The concentrated paste was set on a solid ¹³ C CP / MAS NMR sample stage, and based on the Goldman-Shen pulse sequence, ¹ H 90 ° pulse width 4.5 μs, waiting time 200 μs for initial solvent selection, CP contact time 1 ms The measurement was performed while changing the spin diffusion time from 0.5 to 200 ms. The number of integrations was 4,096 times, and the repetition time was 3 to 10 seconds with 5 times the ¹ H spin-lattice relaxation time of the sample as a guide. The rotation speed of magic angle spinning was 8000 to 10000 Hz depending on the sample.
The peak areas of the pigment and the dispersant are calculated by peak separation of the spectrum at each spin diffusion time, and the diffusion distance L assuming a one-dimensional diffusion model is calculated with respect to the spin diffusion time tm.

The particle structure was judged from a plot of the peak area against the distance from the solvent molecule. When the embedding of the dispersant was recognized by this evaluation, “◯” was given, and when it was not recognized, “X” was given. The results are shown in Table 2A.

(Dispersant uptake rate evaluation)
The pigment dispersion composition was subjected to suction filtration with a membrane filter (MILLIPORE cut size: 0.05 μm). The obtained powder 1 after filtration was put into any appropriate solvent capable of dissolving the incorporated dispersant, and again with a motor mill M-50 (manufactured by Eiger Japan), using zirconia beads having a diameter of 0.65 mm, The dispersion treatment was performed at a peripheral speed of 9 m / s over 3 hours. Thereafter, the dispersant uptake rate was estimated by the following equation from the polymer amount of the powder 2 after filtration and the added polymer amount obtained by suction filtration in the same manner as described above. In addition, the following “amount of polymer containing powder after filtration” is calculated by a difference in mass between “a mass of powder 2 after filtration” and “amount of pigment added below”.
(Dispersant uptake rate) = (Amount of polymer containing powder after filtration) / (Amount of added polymer) × 100
The results are shown in Table 2A (the unit in the table is% by mass).

(Dispersant embedding rate evaluation)
The amount of the polymer containing powder after filtration (mass of powder 2 after filtration−the amount of added pigment) and the mass of pigment added when the pigment is deposited [added pigment amount] The embedding rate of the dispersant was estimated from the following formula.
(Dispersant embedding rate) = (Amount of powder-containing polymer after filtration) / (Amount of added pigment) × 100
The results are shown in Table 2 (the unit in the table is% by mass).

(CR / chronological CR evaluation)
The pigment dispersion composition was applied on a glass substrate at 100 ° C. for 3 minutes so that the thickness of the coating film was 1.4 μm to prepare a sample. Further, the pigment dispersion composition was applied again in the same manner as described above 30 days after the dispersion, and the contrast was measured as follows. The time-dependent contrast change rate was calculated from the time-dependent contrast and the contrast applied and measured immediately after dispersion by the following equation: (Time-dependent change rate) = (initial contrast) / (time-dependent contrast)
The results are shown in Table 2A.

[Contrast measurement]
The obtained pigment dispersion composition samples were each coated on a glass substrate so as to have a thickness of 2 μm, thereby preparing samples. As a backlight unit, a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is used, and two polarizing plates (polarizing plates HLC2-2518 manufactured by Sanritsu Co., Ltd.) are used. ), The amount of transmitted light when the polarization axis is parallel and vertical is measured, and the ratio is defined as the contrast (“1990 Seventh Color Optical Conference, 512-color display 10. 4 ”size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka” etc.) A color luminance meter (BM-5 manufactured by Topcon Corporation) was used for the measurement of chromaticity. Two polarizing plates, a sample, and a color luminance meter are installed at a position 13 mm from the backlight, a polarizing plate is placed at a position 40 mm to 60 mm, a cylinder 11 mm in diameter and 20 mm in length, and the light transmitted through this. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.

[Measurement of average particle size and monodispersity (particle size distribution)]
Using a dispersion sample obtained by diluting the volume average particle size (Mv) to 5 mass% as the particle size (particle size) of the pigment fine particles in the obtained dispersion or composition, Nanotrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) (Trade name). Moreover, the monodispersion degree (Mv / Mn) showing particle size distribution was computed from the number average particle | grain (Mn) measured similarly.

The dispersion compositions 01 to 12 containing the pigment fine particles of the present embodiment exhibit a higher dispersant embedding rate and dispersant uptake rate than the comparative samples c1 to c5, and the amount of the dispersant is smaller than that of the pigment. The amount used is high and the dissociation of the dispersing agent over time is suppressed to maintain a stable dispersion state, thereby achieving a low contrast change rate over time.

(Example A-II, Comparative Example A-II)
<Production of liquid crystal display device>
1. Fabrication of CF by inkjet method and liquid crystal display device using the same [Preparation of photosensitive transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, a light-shielding resin composition K1 having the composition shown in Table 3 below was applied and dried, a thermoplastic resin layer having a dry film thickness of 15 μm on the temporary support, and a dry film thickness of 1. A 6 μm intermediate layer and a light-shielding resin layer having a dry film thickness of 2.4 μm were provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded.
In this way, a photosensitive resin transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the light-shielding resin layer are integrated is prepared, and the sample name is the photosensitive resin transfer material K1. .

* Coating solution for thermoplastic resin layer: Formulation H1
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.4 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) )
= 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.)
5.83 parts by mass / styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight = 10,000, Tg≈100 ° C.) 3.6 parts by mass. 2,2-bis [4- (methacryloxypolyethoxy) phenyl]
Propane (manufactured by Shin-Nakamura Chemical Co., Ltd.)
9.1 parts by mass / surfactant 1 0.54 parts by mass

<Surfactant 1> (Megafac F-780-F (manufactured by Dainippon Ink and Chemicals))) C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ : 40 parts by mass and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ : 55 parts by mass and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ : 5 parts by mass and copolymer (molecular weight 30,000)
30 parts by mass, 70 parts by mass of methyl ethyl ketone

<Intermediate layer (oxygen barrier layer) coating formulation: P1>
-Polyvinyl alcohol ... 32.2 parts by mass (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone ・・・・・・・・・・・ 14.9 parts by mass (PVP, K-30; manufactured by IPS Japan Ltd.)
・ Methanol ・・・・・・・・・・・・・・・・ 429 parts by mass ・ Distilled water ・・・・・・・・・・・.... 524 parts by mass

[Table 3A]

The resin composition K1 having a light-shielding property is first weighed K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then binder 1 and hydroquinone monomethyl. Ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine), Surfactant 1 was weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes.

<K pigment dispersion 1>
・ Carbon black (Degussa, trade name Special Black250)
13.1 parts by mass-Pigment Dispersant A 0.65 parts by mass-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72 parts by mass propylene glycol 79.53 parts by mass of monomethyl ether acetate

<Binder 1>
-Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 40,000)
27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

<DPHA solution>
・ Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ,
Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)
76 parts by mass / propylene glycol monomethyl ether acetate 24 parts by mass

[Formation of light-blocking partition walls]
A non-alkali glass substrate is washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering. After washing with pure water, silane coupling solution (N-β (aminoethyl) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape is a lattice shape, and the radius of curvature of the corner protruding toward the light-shielding partition wall in the portion corresponding to the boundary line between the pixel and the light-shielding partition wall is 0.6 μm.

Next, with a triethanolamine developer (2.5% triethanolamine-containing, nonionic surfactant-containing, polypropylene-based antifoaming agent, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) Shower development was performed at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: Using T-CD1, Fuji Photo Film Co., Ltd., shower development at 29 ° C. for 30 seconds and cone type nozzle pressure of 0.15 MPa to develop a light-shielding resin layer, and patterning separation wall (a partition pattern having a light-shielding property) )

Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent and stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.)”), 33 ° C., 20 seconds, cone type Residue removal was performed with a rotary brush having a shower and nylon hair at a nozzle pressure of 0.02 MPa to obtain a light-shielding partition. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultra-high pressure mercury lamp from the resin layer side, and then heat treated at 240 ° C. for 50 minutes.

[Plasma water repellency treatment]
Thereafter, plasma water repellency treatment was performed by the following method.
Plasma water repellency treatment was performed on the substrate on which the light-shielding partition walls were formed using a cathode coupling parallel plate type plasma processing apparatus under the following conditions.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

[Preparation of inkjet ink for color filter]
An ink-jet ink for a color filter was prepared with the following formulation with reference to Example 1 of JP-A-2002-201387.

<R ink 1>
Pigment dispersion composition 01 51 parts by weight Dipentaerythritol pentaacrylate 2.0 parts by weight Tripropylene glycol diacrylate 4.5 parts by weight 2-methyl-1- [4- (methylthio) phenyl]
-2-Monfolinopropen-1-one 2.0 parts by mass Diethylene glycol monobutyl ether acetate,
29.9 dyn / cm 44 parts by mass

<R ink 2 to 12, R ink c1 to c5>
R inks 2 to 12 and R inks c1 to c5 were prepared in the same manner except that 02 to 12 and c1 to c5 were used instead of the pigment dispersion composition 01 of R ink 1.

<G ink 1>
G pigment (C.I.P.B.36) 6.0 parts by mass Polymer dispersant (Solsperse 24000, manufactured by AVECIA)
2.0 parts by weight binder (benzyl methacrylate-methacrylic acid copolymer)
4.6 parts by mass Dipentaerythritol pentaacrylate 2.0 parts by mass Tripropylene glycol diacrylate 5.0 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-
Monforinopropen-1-one 2.0 parts by mass diethylene glycol monobutyl ether acetate,
29.9 dyn / cm 80 parts by mass

<B ink 1>
G pigment (C.I.P.B.15.6) 6.0 parts by mass Polymer dispersant (Solsperse 24000, manufactured by AVECIA)
2.0 parts by weight binder (benzyl methacrylate-methacrylic acid copolymer)
4.6 parts by mass Dipentaerythritol pentaacrylate 2.0 parts by mass Tripropylene glycol diacrylate 5.0 parts by mass 2-methyl-1- [4- (methylthio) phenyl] -2-
Monforinopropen-1-one 2.0 parts by mass diethylene glycol monobutyl ether acetate,
29.9 dyn / cm 80 parts by mass

Regarding the mixing of each component in Table 3 above, first, a pigment and a polymer dispersant were added to a part of the solvent, mixed, and stirred using a three roll and bead mill to obtain a pigment dispersion. On the other hand, other blending components were added to the remainder of the solvent, and dissolved and dispersed by stirring to obtain a binder solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the binder solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

Each of the R inks obtained above was applied on a glass substrate at 100 ° C. for 10 minutes so as to have a coating film thickness of 2.0 μm to prepare a sample. The contrast of the prepared sample was measured in the same manner as in Example AI. Further, the R ink was applied again in the same manner as described above 30 days after dispersion, and the contrast was measured. The rate of change with time was calculated from this time-dependent contrast and the contrast applied and measured immediately after fabrication. The results at that time are shown in Table 4A.

It can be seen that the ink-jet inks (R inks 1 to 12) of the present embodiment have both a high initial contrast and a low contrast change rate over time as compared with the comparative sample R inks c1 to c5.

(Example A-III, Comparative Example A-III)
[Pixel formation]
The R ink 1, G ink 1, and B ink 1 obtained above were first ejected into a recess surrounded by a light-shielding partition as follows using a piezo type head. And the color filter of this invention was obtained as follows.
The head has a nozzle density of 150 per 25.4 mm, and has 318 nozzles. By fixing these two nozzles in the nozzle row direction with a shift of 1/2 the nozzle interval, 25 heads are arranged on the substrate in the nozzle array direction. . 300 drops per 4 mm.
The head and ink are controlled so that the vicinity of the ejection portion is 50 ± 0.5 ° C. by circulating hot water in the head.
Ink ejection from the head is controlled by a piezo drive signal applied to the head, and ejection of 6 to 42 pl per droplet is possible. In this embodiment, the head is moved while the glass substrate is conveyed at a position 1 mm below the head. More drops. The conveyance speed can be set in the range of 50 to 200 mm / s. The piezo drive frequency can be up to 4.6 kHz, and the droplet ejection amount can be controlled by these settings.

Each of R, G, and B is desired by controlling the conveying speed and the driving frequency so that the coating amount of the pigment is 1.1 g / m ² , 1.8 g / m ² , and 0.75 g / m ^2. R, G, and B inks were ejected into the recesses corresponding to R, G, and B.
The ejected ink is conveyed to an exposure unit and exposed by an ultraviolet light emitting diode (UV-LED). As the UV-LED, NCCU033 (trade name) manufactured by Nichia Corporation was used. This LED outputs ultraviolet light having a wavelength of 365 nm from one chip. When a current of about 500 mA is applied, light of about 100 mW is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 W / cm ² can be obtained on the surface. The exposure time after the droplet ejection and the exposure time can be changed according to the transport speed of the medium and the distance between the head and the LED in the transport direction. After landing, the film was dried at 100 degrees for 10 minutes and then exposed.
Depending on the setting of the distance and the conveyance speed, the exposure energy on the medium can be adjusted between 0.01 and 15 J / cm ² . The exposure energy was adjusted according to the conveyance speed.
For measurement of these exposure power and exposure energy, a spectroradiometer URS-40D (trade name) manufactured by USHIO ELECTRIC CO., LTD. Was used, and a value obtained by integrating between wavelengths 220 nm and 400 nm was used.
The glass substrate after droplet ejection was baked in an oven at 230 ° C. for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.

[Production of liquid crystal display devices]
A liquid crystal display device was produced using the produced color filter (referred to as color filter III01) and the display characteristics were evaluated.
(Formation of ITO electrode)
The glass substrate on which the color filter is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed.
(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

<Positive photosensitive resin layer coating solution formulation>
・ Positive resist solution (FH-2413F manufactured by FUJIFILM Electronics Materials Co., Ltd.)
: 53.3 parts by mass / Methyl ethyl ketone: 46.7 parts by mass / Megafac F-780F (Dainippon Ink Chemical Co., Ltd.)
: 0.04 parts by mass

(Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate. did.

The color filter III02 is exactly the same as the color filter and the liquid crystal display device, except that the R ink 1 used in manufacturing the liquid crystal display device III01 from the color filter III01 is changed to R inks 2 to 12 and c1 to c5, respectively. To III12, IIIc1 to IIIc5 and liquid crystal display devices III0 to III12 and IIIc1 to IIIc5 were prepared and evaluated in the same manner.

<Evaluation of ink and liquid crystal display device>
[Evaluation of display characteristics]
The liquid crystal display device substrate was taken out from the liquid crystal display device, and the contrast was measured in the same manner as in Example AI to evaluate the display characteristics of the liquid crystal display device.

The color filter and liquid crystal display device produced using the color filter inkjet ink of this embodiment showed high contrast. Furthermore, the liquid crystal display device of the present invention can express black with little leakage light during black display, and as a result, exhibits high descriptive power.

2. Production of CF with colored photosensitive resin composition and liquid crystal display device using the same (Example A-IV, Comparative Example A-IV)
The pigment dispersion composition 01 was mixed with other components so as to have the composition shown in Table 5A below to prepare a colored photosensitive resin composition 01 for a color filter.

[Table 5A]

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, molecular weight 40,000)
27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass <Surfactant 2>
・ The following structure 1 30 mass parts ・ Methyl ethyl ketone 70 mass parts

Colored photosensitive resin compositions for color filters 02 to 12, and c1 to c5 were prepared in the same manner as described above except that the pigment dispersion compositions 02 to 12 and c1 to c5 were used instead of the pigment dispersion composition 01, respectively. did.
The colored photosensitive composition for producing the color filter was applied on a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. The contrast of the prepared sample was measured in the same manner as in Example AI. Furthermore, the colored photosensitive composition was applied again in the same manner as described above 30 days after dispersion, and the contrast was measured. The rate of change with time was calculated from this time-dependent contrast and the contrast applied and measured immediately after fabrication. Table 6 shows the results at that time. The results are shown in Table 6A below.

As shown in Table 6A, the colored photosensitive resin compositions for color filters 01 to 12 of the present invention achieve both a high contrast and a low contrast change rate as compared with the comparative samples c1 to c5.

(Examples AV and Comparative Examples AV)
[Preparation of color filter (preparation by application using slit nozzle)]
[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 7A below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K2 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K2 was obtained. In addition, the preparation procedure of the colored photosensitive resin composition K2 is the same as the procedure of the previous resin composition K1.

[Table 7A]

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, and then a KOH-based developer (KOH, containing a nonionic surfactant, trade name: CDK-1, (Fuji Film Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

<K pigment dispersion 2>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass-Dispersant (compound 2J below) 0.65 parts by mass-polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000)
6.72 parts by mass-79.53 parts by mass of propylene glycol monomethyl ether acetate

<Binder 3>
-Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000)
27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

[Formation of red (R) pixels]
A heat-treated pixel R was formed on the substrate on which the image K was formed using the colored photosensitive resin composition R1 having the composition shown in Table 8A below in the same process as the formation of the black (K) image. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 8A]

<R pigment dispersion composition 01>
-Pigment dispersion composition 01 of Example A-1 (C.I.P.R.254)
11 parts by mass Propylene glycol monomethyl ether acetate 68.2 parts by mass <R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 30,000)
12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition described in Table 9A below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 9A]

As the G pigment dispersion 1, “trade name: GT-2” manufactured by Fuji Film Electronics Materials Co., Ltd. was used. As the Y pigment dispersion 1, “trade name: CF Yellow EX3393” manufactured by Mikuni Color Co., Ltd. was used.

[Formation of blue (B) pixels]
A colored photosensitive resin composition B1 having the composition shown in Table 10A below is used on the substrate on which the image K, the pixel R, and the pixel G are formed, and is heat-treated in the same process as the formation of the black (K) image. Pixel B was formed, and the target color filter A was obtained. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 10A]

As B pigment dispersion 1, “trade name: CF Bull-EX3357” manufactured by Mikuni Dye Co., Ltd. was used. As the B pigment dispersion 2, “trade name: CF Bull-EX3383” manufactured by Mikuni Dye Co., Ltd. was used.

<Binder 4>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = random copolymer of 36/22/42 molar ratio, molecular weight 38,000)
27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass

Instead of the pigment composition 01 used for the R pigment dispersion 01, R pigment dispersions 02 to 12, and c1 to c5 were prepared using the pigment compositions 02 to 12, and c1 to c5, respectively. Then, the color filters V02 to V12 and Vc1 to Vc5 are prepared in the same manner as the above-described method for producing the color filter V01 except that R pigment dispersions V02 to V12 and Vc1 to Vc5 are used instead of the R pigment dispersion 01, respectively. Produced.

[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was prepared using each of the above color filters, and the display characteristics were evaluated.
(Formation of ITO electrode)
The color filter was put in a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) was vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO to form an ITO transparent electrode.
(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

(Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate. did.

[Production and Evaluation of Liquid Crystal Display]
The liquid crystal display device substrate was taken out from the liquid crystal display device V01, and the contrast was measured in the same manner as in Example AI.

Liquid crystal display devices V02 to V12 and Vc1 to c5 were produced in the same manner except that the color filter V01 was changed to the color filters V02 to V12 and Vc1 to c5, respectively, and evaluated in the same manner.

The color filter and liquid crystal display device produced using the color filter inkjet ink of this embodiment showed high contrast. In addition, it was possible to express black with little leakage light when displaying black, and as a result, it showed high descriptive power.

(Example A-VI, Comparative Example A-VI)
(Example A-10)
Pigment Green 36, Pigment Green 58, Pigment Blue 15: 6, Pigment Blue 79, Pigment Blue 80, and Pigment Yellow 185 are used in place of Pigment Red 254 in the preparation of Pigment Dispersion Composition 01 in Example 1, respectively. Dispersion compositions O, P, Q, R, S, and T were prepared.
As for the pigment dispersion compositions O, P, Q, R, S, and T, the dispersant embedding rate and the dispersant uptake rate were calculated in the same manner as in Example AI. As a result, all the pigment dispersion compositions were 5%. The above dispersant embedding rate and 10% or more dispersant uptake rate were shown. Further, when the contrast and the change in contrast with time were measured in the same manner as in Example AI, each dispersion composition showed a high contrast and a low rate of change in contrast with time.
On the other hand, a pigment composition for comparison was prepared in the same manner as in Comparative Example I using the pigment types used in Pigment Dispersion Compositions O, P, Q, R, S, and T. The contrast was lower than that, and the contrast greatly decreased over time.

Example A-11
<Preparation of pigment dispersion composition U>
[Preparation of pigment dispersion]
To 1000 ml of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.), C.I. I. A pigment solution U was prepared by adding 50 g of Pigment Violet 23 (Hostaperm Violet RL-NF Clariant) and 30.0 g of the graft polymer P-1. As a result of measuring the viscosity of this pigment solution T using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment solution T is 45.0 ° C. is 86. 2 mPa · s. Separately from this, 1600 ml of water was prepared as a poor solvent.
Here, the temperature of the solution was controlled at 25 ° C., and the pigment solution M was added to NP-KX-500 in 1600 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Organic pigment particles are formed by injecting 100 ml at a flow rate of 70 ml / min from a liquid feed pipe having a channel diameter of 0.25 mm using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) Dispersion U was prepared. The Reynolds number under this condition is 92.
The pigment nanoparticle dispersion prepared by the above method was concentrated at 3000 rpm for 90 minutes using an H-122 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type ro cloth manufactured by Shikishima Canvas Co., Ltd. The pigment nanoparticle concentrated paste was recovered.
The pigment nanoparticle concentrated paste was subjected to solvent removal at 100 ° C. on a hot plate to obtain an organic pigment powder U (solid content concentration: 96 mass%).

A pigment dispersion composition U having the following composition was prepared using the pigment powder.
Organic pigment powder U 8.8g
Propylene glycol monomethyl ether acetate 36.7g
The pigment dispersion composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

As a result of calculating the dispersant embedding rate and the dispersant uptake rate for the pigment dispersion composition U in the same manner as in Example AI, all the pigment dispersion compositions had a dispersant embedding rate of 5% or more and 10%. The above dispersant uptake rate was shown. Further, when the contrast and temporal change in contrast were measured in the same manner as in Example 1, all the dispersion compositions showed high contrast and low contrast change rate with time.
On the other hand, a pigment composition for comparison was prepared in the same manner as in Comparative Example AI using the pigment type used in Pigment Dispersion Composition U. However, the contrast was lower than that of the above Examples, and The contrast greatly decreased with time.

B. Examples and Comparative Examples according to Second Embodiment (Example BI, Comparative Example BI)
(Synthesis Example 1B)
(Synthesis of Monomer M-1)
45.28 parts of 2-thiobarbituric acid and 13.82 parts of sodium hydroxide are dissolved in 200 parts of dimethyl sulfoxide and heated to 25 ° C. To this, 57.53 parts of chloromethylstyrene is dropped, and the mixture is further heated and stirred at 55 ° C. for 5 hours. After heating and stirring, 150 parts of methanol and 150 parts of distilled water are added to the reaction solution and stirred for 1 hour. Subsequently, this solution is poured into 2000 parts of distilled water while stirring, and the resulting precipitate is filtered and washed. As a result, 80.1 parts of the monomer M-1 was obtained.

(Synthesis of polymer PB-1)
The following monomer solution is introduced into a nitrogen-substituted three-necked flask and stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor). To do. Then, the following initiator solution is added to said liquid, and it heat-stirs at 78 degreeC for 2 hours. The following initiator solution is further added after heating and stirring, and the operation of heating and stirring at 78 ° C. for 2 hours is repeated twice in total. After the last 2 hours of stirring, the mixture is subsequently heated and stirred at 90 degrees for 2 hours. The obtained reaction solution was poured into 1500 parts of isopropanol while stirring, and the resulting precipitate was collected by filtration and dried by heating to obtain a graft polymer PB-1.

(Monomer solution)
Monomer M-1 4.0 parts AA-6 16.0 parts Methacrylic acid 3.0 parts 1-methyl-2-pyrrolidone 46.0 parts

(Initiator solution)
2.2'-azobis (isobutyric acid) dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.1 part 1-methyl-2-pyrrolidone 2 parts

(Synthesis Examples 2B-18B)
Polymers PB-2 to PB-18 were obtained in the same manner as in Synthesis Example 1B, except that the monomer composition and initiator composition shown in Synthesis Example 1B were changed to Table 1B.

AA-6: One-terminal methacryloylated polymethyl methacrylate oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
AB-6: One-terminal methacryloylated poly-n-butyl methacrylate oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
AS-6: One-end methacryloylated polystyrene oligomer (Mn = 6000, manufactured by Toa Gosei Chemical Co., Ltd.)
PE-350; Bremer PE-350 (trade name), polyethylene glycol monomethacrylate (manufactured by NOF Corporation)
PP-1000; BLEMMER PP-1000 (trade name), polypropylene glycol monomethacrylate (manufactured by NOF Corporation)
PEP-350B; Bremmer 70PEP-350B (trade name), polyethylene glycol polypropylene glycol monomethacrylate (manufactured by NOF Corporation),
FM5: Plaxel FM5 (trade name), polycaprolactone monomethacrylate (manufactured by Daicel Chemical Industries, Ltd.)

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
StMA: Stearyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
DMA: dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
HexMA: Hexyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
NMP; 1-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.)

Example B-1
To 1000 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries), pigment C.I. I. 50 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) is dispersed, and 52.3 g of a tetramethylammonium hydroxide 25% methanol solution is added dropwise to prepare a pigment solution. did. 30.0 g of graft polymer PB-1 was dissolved in 90 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), and 16.7 g of a 25% methanol solution of tetramethylammonium hydroxide was added dropwise to prepare a polymer solution A. did. The pigment solution and the polymer solution A were mixed to prepare a pigment / polymer solution A. As a result of measuring the viscosity of this pigment / polymer solution A using Viscomate VM-10A-L (trade name, manufactured by CBC Materials), the viscosity when the liquid temperature of the pigment polymer solution A is 24.5 ° C. Was 17.1 mPa · s. Separately, 1000 ml of ion-exchanged water containing 19 g of 1 mol / l hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent.
Here, the temperature was controlled at 5 ° C., and the pigment / polymer solution A was added to 1000 ml of ion-exchanged water containing hydrochloric acid as a poor solvent stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Is injected with 100 ml at a flow rate of 400 ml / min from a liquid feed pipe having a flow path diameter of 1.1 mm using a NP-KX-500 large capacity non-pulsating pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). Particles were formed to prepare pigment nanoparticle dispersion liquid A.

The pigment nanoparticle dispersion liquid A prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type ro cloth manufactured by Shikishima Canvas Co., Ltd. The resulting pigment nanoparticle concentrated paste A was recovered.
The pigment nanoparticle concentrated paste A was dried in an oven at 100 ° C. for 8 hours to obtain an organic pigment powder A (solid content concentration: 97 mass%) (organic pigment content: 58 mass%).

Using the organic pigment powder A, a pigment dispersion composition A having the following composition was prepared.
14.0 g of the organic pigment powder A
46.8g of propylene glycol monomethyl ether acetate

Pigment dispersion composition A having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. Obtained.

(Examples B-2 to B-9)
In the pigment dispersion composition of Example B-1, pigment dispersion compositions B to O were prepared in the same manner as in Example 1 except that the graft polymer was changed to PB-2 to 15.

(Comparative Example B-1)
Sodium chloride and pigment C.I. in 1,3 butylene glycol diacetate solution. I. 10 g of powder of Pigment Red 254 (trade name: Irgaphor Red BT-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 30.0 g of graft polymer PB-1 were charged in a double arm kneader and kneaded at 80 ° C. for 15 hours. After kneading, the mixture was taken out into 700 parts by mass of a 1% hydrochloric acid aqueous solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized. Then, 2.4 g of propylene glycol monomethyl ether acetate was added to 1 g of the pulverized product and mixed. The pigment composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm to obtain a pigment dispersion composition P.

(Comparative Example B-2)
A pigment dispersion composition Q was prepared in the same manner as in Example B-1, except that the graft polymer of Example B-1 was changed to PB-17.

(Comparative Example B-3)
To 1000 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries), pigment C.I. I. 50 g of Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 30.0 g of PB-18 are dispersed in this solution. 3 g was dropped to prepare a pigment solution. Separately, 1000 ml of ion-exchanged water was prepared as a poor solvent.
Here, the temperature of the solution was controlled at 5 ° C., and the pigment solution was added to 1000 ml of ion-exchanged water containing hydrochloric acid as a poor solvent stirred at 500 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Using a KX-500 type large capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.), by injecting 100 ml at a flow rate of 400 ml / min from a liquid feed pipe having a flow path diameter of 1.1 mm, Then, a pigment nanoparticle dispersion liquid R was prepared. Subsequently, 5% sulfuric acid aqueous solution was added dropwise to the pigment nanoparticle dispersion R to adjust the pH to 4.0, thereby preparing a pigment nanoparticle aggregate.
The pigment nanoparticle aggregated liquid prepared by the above procedure was concentrated at 5000 rpm for 90 minutes using an H-112 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type cloth manufactured by Shikishima Canvas Co., Ltd. The pigment nanoparticle concentrated paste was recovered.
The pigment nanoparticle concentrated paste was dried in an oven at 100 ° C. for 8 hours to obtain an organic pigment powder R (solid content concentration 94 mass%) (organic pigment content 59 mass%).

Using the organic pigment powder R, a pigment dispersion composition R having the following composition was prepared.
The organic pigment powder R 14.0 g
46.8g of propylene glycol monomethyl ether acetate
Pigment dispersion composition A having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 10 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. Obtained.

(Comparative Example B-4)
In the pigment dispersion composition of Example B-1, Pigment Dispersion Composition S was prepared in the same manner as in Example B-1, except that the graft polymer was polystyrene.

(Comparative Example B-5)
In the pigment dispersion composition of Example B-1, pigment dispersion composition T was prepared in the same manner as in Example B-1, except that the graft polymer was polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.). Was prepared.

(Reference example)
A pigment dispersion composition U was prepared in the same manner as in Example B-1, except that the graft polymer of Example B-1 was changed to PB-16.

[Measurement and evaluation of dispersant uptake rate]
Same as Example AI.

[Evaluation of dispersant embedding rate]
Same as Example AI.

[Measurement and evaluation of surface uneven distribution]
The intraparticle distribution of the dispersant was confirmed using solid state ¹³ C CP / MAS NMR measurement (AVANCE DSX-300 spectrometer [trade name] and 4 mmφ HFX CP / MAS probe manufactured by Bruker BioSpin). The solid ¹³ C CP / MAS NMR measurement was performed as follows.
The pigment dispersion compositions A to U are each suction filtered using a membrane filter (MILLIPORE cut size: 0.05 μm), and further washed with a dispersion solvent to prepare a concentrated paste. The concentrated paste was set on a solid ¹³ C CP / MAS NMR sample stage, and based on the Goldman-Shen pulse sequence, ¹ H 90 ° pulse width 4.5 μs, waiting time 200 μs for initial solvent selection, CP contact time 1 The measurement was carried out by changing the spin diffusion time from 0.5 to 200 ms. The number of integrations was 4,096 times, and the repetition time was 3 to 10 seconds with 5 times the ¹ H spin-lattice relaxation time of the sample as a guide. The rotation speed of magic angle spinning was 8000 to 10,000 Hz depending on the sample.
The peak areas of the pigment and the dispersant are calculated by peak separation of the spectrum at each spin diffusion time, and the diffusion distance L assuming a one-dimensional diffusion model is calculated with respect to the spin diffusion time t _m .

From the plot of the peak area against the distance from the solvent molecule, the ratio r ₂ / R of the distance from the particle surface where 80% by mass of the total amount of the dispersant present in the particle is present (FIG. 1). -2) (* 1 in the table) was calculated.

[Measurement and evaluation of outward extension rate]
Confirmation of the extent of outward extension of the steric repulsion chain (outward extension rate) was carried out by solid-state ¹³ C CP / MAS NMR measurement (AVANCE DSX-300 spectrometer [trade name] manufactured by Bruker BioSpin Co., Ltd.) and 4 mmφ HFX CP / MAS probe). The solid ¹³ C CP / MAS NMR measurement was performed as follows.
The pigment dispersion compositions A to U are each suction filtered using a membrane filter (MILLIPORE cut size: 0.05 μm), and further washed with a dispersion solvent to prepare a concentrated paste. The concentrated ¹³ C CP / MAS NMR measurement of the concentrated paste is performed to measure the peak intensity derived from the steric repulsion chain. Next, the concentrated paste is dried at 100 ° C. for 8 hours to produce a dry powder, and similarly, the peak intensity derived from the steric repulsion chain is measured from solid ¹³ C CP / MAS NMR measurement, and the ratio of each peak intensity is excluded. Estimated the extension rate. (Outward extension ratio) = (Stereo-repulsive chain-derived peak intensity in concentrated paste) / (Stereo-repulsive chain-derived peak intensity in dry powder) × 100. The results are shown in Table 2B (the unit in the table is% by mass).

[CR / chronological CR evaluation]
The pigment dispersion compositions A to U were each coated on a glass substrate at 100 ° C. for 3 minutes so that the thickness of the coating film was 1.4 μm, and samples were prepared (with regard to the contrast measurement method). The pigment dispersion compositions A to U were applied again in the same manner as described above 30 days after the dispersion, and the contrast was measured, and the time-dependent contrast and the contrast applied and measured immediately after dispersion were used to determine the time. The contrast change rate was calculated (contrast change rate with time) = (initial contrast) / (contrast with time), and the results at that time are shown in Table 2B.

[Contrast measurement]
Same as Example AI.

[Measurement of average particle size and monodispersity (particle size distribution)]
Same as Example AI.

* 1: Radial distance ratio (r ₂ / R) that separates the outer region Ao and the inner region Ai where the embedding dispersant is 80% or more.
* 2: Outer region segmentation rate of 0% refers to a state in which the dispersant is not present in the particle and all the parts of the dispersant are outside the particle.

The dispersion composition of pigment fine particles (embodiment, reference example) using an embedding dispersant having a specific interaction group attracting to the pigment compound showed a higher dispersant uptake rate than other samples. In addition, the dispersion composition of the fine pigment particles of the example in which the structural part having the steric repulsive group is applied to the embedding dispersant is different from the comparative example and the reference example, and the dispersant is unevenly distributed on the outer side of the particle. Buried. As a result, it is considered that high dispersion stability is achieved even with a small amount of dispersant used with respect to the pigment, achieving both a high initial contrast and a low rate of contrast change over time. I understand that.

(Example B-II, Comparative Example B-II)
Preparation of colored photosensitive resin composition Color dispersion photosensitive resin composition A for color filters was prepared by mixing pigment dispersion composition A with other components so as to have the composition shown in Table A below.

[Table A]

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 38/25/37 molar ratio random copolymer, molecular weight 40,000)
27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass <Surfactant 2>
-30 parts by mass of the structure 1-70 parts by mass of methyl ethyl ketone

Colored photosensitive resin compositions B to U for color filters were prepared in the same manner as described above except that pigment dispersion compositions B to U were used instead of pigment dispersion composition A, respectively.
The colored photosensitive compositions A to U for color filter preparation were applied on a glass substrate using a spin coater and dried at 100 ° C. for 2 minutes to form a film having a thickness of about 2 μm. The contrast of the prepared sample was measured in the same manner as in Example B-1. Further, the colored photosensitive compositions A to N were applied again in the same manner as described above 30 days after dispersion, and the contrast was measured. The rate of change with time was calculated from this contrast with time and the contrast applied and measured immediately after production (rate of change with time) = (initial contrast) / (contrast with time). The results at that time are shown in Table 3B.

[Table 3B]

As shown in Table 3B, the colored photosensitive resin composition for color filters (Examples) using the fine particles of this embodiment has both a high contrast and a low rate of change with time compared to the comparative sample (Comparative Example). It can be seen that both good dispersibility and stability over time are achieved.

(Example B-III, Comparative Example B-III)
[Production of color filters and liquid crystal display devices (production by application using slit-like nozzles)]
[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 4B below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K2 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K2 was obtained. In addition, the preparation procedure of the colored photosensitive resin composition K2 is the same as the procedure of the previous resin composition K1.

[Table 4B]

<K pigment dispersion 2>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan Co., Ltd.)
13.1 parts by mass-Dispersant (compound 2J) 0.65 parts by mass-polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000)
6.72 parts by mass-79.53 parts by mass of propylene glycol monomethyl ether acetate

[Formation of red (R) pixels]
A heat-treated pixel R was formed on the substrate on which the image K was formed using the colored photosensitive resin composition R1 having the composition described in Table 5B below, in the same process as the formation of the black (K) image. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 5B]

<R pigment dispersion composition A>
-11 parts by mass of pigment dispersion composition A (CIPR 254) of Example 1-68.2 parts by mass of propylene glycol monomethyl ether acetate <R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 30,000)
12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition described in Table 6B below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 6B]

[Formation of blue (B) pixels]
The substrate on which the image K, the pixel R, and the pixel G are formed uses the colored photosensitive resin composition B1 having the composition described in Table 7BE below, and is heat-treated in the same process as the formation of the black (K) image. Pixel B was formed, and the target color filter A was obtained. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. The procedure for preparing the colored photosensitive resin composition is the same as that for the colored photosensitive resin composition K2.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 7B]

Instead of pigment composition A used for R pigment dispersion A, R pigment dispersions B to U were prepared using pigment compositions B to U, respectively. Then, color filters B to U were produced in the same manner as the production method of the color filter A except that R pigment dispersions B to U were used instead of the R pigment dispersion A, respectively. The contrast of the produced color filters A to U was measured in the same manner as in Example B-1. Further, after 30 days of dispersion of the colored photosensitive compositions A to U, a color filter was prepared again by the same method as described above, and the temporal contrast was measured. The rate of change with time was calculated from this time-dependent contrast and the contrast applied and measured immediately after fabrication.

[Table 8B]

[Production and Evaluation of Liquid Crystal Display]
A liquid crystal display device was manufactured using the color filters A to U, and the display characteristics were evaluated.
(Formation of ITO electrode)
The color filter A was put in a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) was vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO to form an ITO transparent electrode. .
(Spacer formation)
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
(Formation of liquid crystal alignment control protrusions)
A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .

Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal alignment control projection on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display substrate.

(Creation of liquid crystal display device)
An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above.
After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) is constructed and arranged on the back side of the liquid crystal cell provided with the polarizing plate. did.

Liquid crystal display devices B to U were produced in the same manner except that the color filter A was changed to the color filters B to U, respectively, and evaluated in the same manner. As a result, it was confirmed that the liquid crystal display devices A to O provided with the color filter produced using the fine particles of the present embodiment showed high contrast, and as a result, the blackness was good and the drawing power was high.

(Example B-IV, Comparative Example B-IV)
(Example B-16)
By using Pigment Green 36, Pigment Green 58, Pigment Blue 15: 6, Pigment Blue 79, Pigment Blue 80, and Pigment Yellow 185 instead of Pigment Red 254 in the preparation of Pigment Dispersion Composition A in Example 1 In the same manner as in Example B-1, pigment dispersion compositions V, W, X, Y, Z and AA were prepared.
The pigment dispersion compositions V, W, X, Y, Z, and AA were measured for the dispersant uptake rate and outward uneven distribution in the same manner as in Example BI. As a result, all the pigment dispersion compositions showed 10%. The dispersion agent uptake ratio exceeded, and 80% by mass or more of the embedded dispersant was unevenly distributed in the outer region from the particle surface of the fine particles to 50% of the particle radius. Further, when the contrast and the change in contrast with time were measured in the same manner as in Example BI, all the dispersion compositions showed high contrast and low contrast change rate with time.
On the other hand, a pigment composition for comparison was prepared in the same manner as B-1 to B-5 in Comparative Example BI, using the pigment types used in Pigment Dispersion Composition V, W, X, Y, Z, and AA. Each of them was produced, but the contrast was lower than that of the above example, and the contrast was significantly lowered with time.

(Example B-17)
<Preparation of pigment dispersion composition AB>
[Preparation of pigment dispersion]
To 1000 g of methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.), C.I. I. Pigment violet 23 (Hostaperm Violet RL-NF manufactured by Clariant) 50 g and graft polymer P-1 30.0 g were added to prepare pigment solution AB. The viscosity of this pigment solution AB was measured using Viscomate VM-10A-L (trade name, manufactured by CBC Materials). As a result, the viscosity when the liquid temperature of the pigment solution AB was 45.0 ° C. was 84.degree. It was 5 mPa · s. Separately from this, 1600 ml of water was prepared as a poor solvent.
Here, the temperature of the solution was controlled at 25 ° C., and the pigment solution M was added to NP-KX-500 in 1600 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). Organic pigment particles are formed by injecting 100 ml at a flow rate of 70 ml / min from a liquid feed pipe having a channel diameter of 0.25 mm using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) Dispersion AB was prepared. Note that the Reynolds number under this condition is 89.
The pigment nanoparticle dispersion prepared by the above method was concentrated at 3000 rpm for 90 minutes using an H-122 type centrifugal filter manufactured by Kokusan Co., Ltd. and a P89C type ro cloth manufactured by Shikishima Canvas Co., Ltd. The pigment nanoparticle concentrated paste was recovered.
The pigment nanoparticle concentrated paste was solvent-removed on a hot plate at 100 ° C. to obtain an organic pigment powder AB (solid content concentration 96% by mass).

A pigment dispersion composition AB having the following composition was prepared using the pigment powder.
Organic pigment powder AB 8.8g
Propylene glycol monomethyl ether acetate 36.7g
The pigment dispersion composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

The pigment dispersion composition AB was measured for the dispersant uptake rate and outward distribution in the same manner as in Example BI. As a result, all of the pigment dispersion compositions showed a dispersant uptake rate of more than 10%. More than 80% by mass of the encapsulated dispersant was unevenly distributed in the outer region from the particle surface of the fine particles to 50% of the particle radius. Further, when the contrast and the change in contrast with time were measured in the same manner as in Example BI, all the dispersion compositions showed high contrast and low contrast change rate with time.
On the other hand, a pigment composition for comparison was prepared in the same manner as B-1 to B-5 in Comparative Example BI using the pigment type used in Pigment Dispersion Composition AB. The contrast was lower than that, and the contrast greatly decreased over time.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application includes Japanese Patent Application No. 2008-241805 filed in Japan on September 19, 2008, Japanese Patent Application No. 2008-241810 filed in Japan on September 19, 2008, and May 26, 2009. Claiming priority based on Japanese Patent Application No. 2009-126242 filed in Japan, the contents of which are both incorporated herein by reference.

1 Water-insoluble compound (continuous phase)
2 Embedding dispersant (dispersed phase)
10, 20 Fine particles of water-insoluble compounds

Claims

When mixing the solution in which the water-insoluble compound is dissolved in the good solvent and the poor solvent, (i) mixing the both solutions by dissolving the dispersant on the good solvent side and / or the poor solvent side, or (ii) Apart from these, fine particles embedding the dispersant, prepared by preparing a solution in which the dispersant is dissolved in a good solvent and mixing together with the two solutions,
Fine particles of a water-insoluble compound, wherein the dispersant is embedded in an amount of 5 to 200% by mass based on the mass of the water-insoluble compound.
The fine particles according to claim 1, wherein 10% by mass or more and 100% by mass or less of the dispersant dissolved at the time of fine particle formation is taken in and embedded in the fine particles.
The fine particles according to claim 1 or 2, wherein the total amount of the dispersant dissolved in the good solvent and the poor solvent is 10 to 300 parts by mass with respect to 100 parts by mass of the water-insoluble compound.
In the fine particles composed of a water-insoluble compound and a dispersant, 80% by mass or more of the dispersant embedded in the fine particles out of the dispersant is from the particle surface of the fine particles to 50% of the particle radius. Fine particles of a water-insoluble compound characterized by being unevenly distributed in the outer region of
When the fine particles are mixed with a poor solvent and a solution in which the water-insoluble compound is dissolved in a good solvent, (i) the two solutions are mixed with the dispersant contained on the good solvent side and / or the poor solvent side. Or (ii) a build-up fine particle embedding the dispersant, prepared by preparing a solution in which the dispersant is dissolved in a good solvent separately from these and mixing with the two solutions. The fine particles according to claim 4.
6. The fine particles according to claim 4, wherein the dispersant is embedded in an amount of 5 to 200% by mass based on the mass of the water-insoluble compound.
The fine particle according to any one of claims 1 to 6, wherein the dispersant is a polymer dispersant having a mass average molecular weight of 1000 or more.
The fine particle according to any one of claims 1 to 7, wherein the dispersant is a polymer dispersant having at least one heterocyclic hydrocarbon group in the molecule.
The polymer dispersant having a structural portion exhibiting an interaction attracting the water-insoluble compound composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group. Item 9. The fine particle according to any one of Items 1 to 8.
The dispersant has at least one hydrophilic group selected from the group consisting of a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, an amide group, a sulfonamide group, and an alkylene oxide group. The fine particles according to any one of claims 1 to 9.
The dispersant further includes a site having at least one bond selected from an ester bond, an ether bond, and an amide bond, or a site having an aromatic ring, for dispersing the water-insoluble compound in a dispersion medium. The fine particle according to claim 9 or 10, which is a polymer dispersant having a steric repulsion part having a repeating unit.
The fine particles according to claim 11, wherein the steric repulsive portion of the embedded dispersant extends outward from the fine particles.
The fine particles according to any one of claims 1 to 7, wherein the water-insoluble compound is a pigment.
The good solvent is at least one solvent selected from the group consisting of an acidic solvent, an alkaline solvent, a polar organic solvent, and a supercritical fluid, or a mixture thereof. Fine particles described in 1.
The fine particles according to any one of claims 1 to 14, wherein the poor solvent is a solvent containing water as a main component.
The fine particles according to any one of claims 1 to 15, wherein the average particle size is 100 nm or less.
The main component comprises (a) an aqueous medium, (b) an organic solvent selected from an ester compound solvent, a ketone compound solvent, and an alcohol compound solvent, and (c) at least one selected from the group consisting of a reactive diluent. A fine particle dispersion of a water-insoluble compound, wherein the fine particles according to any one of claims 1 to 16 are dispersed in a solvent.
The fine particle dispersion according to claim 17, further comprising a dispersant that is not embedded in the fine particles.
The fine particle dispersion according to claim 17 or 18, wherein the fine particle dispersion is used for producing a resist or an ink formed on a substrate.
When mixing the solution in which the water-insoluble compound is dissolved in the good solvent and the poor solvent, (i) mixing the both solutions by dissolving the dispersant on the good solvent side and / or the poor solvent side, or (ii In addition to these, when preparing a solution in which a dispersant is dissolved in a good solvent and mixing with both the liquids to produce fine particles of the water-insoluble compound,
A polymer dispersing agent having a structural part that exhibits an interaction attracting a water-insoluble compound is used as the dispersing agent, and 10% by mass or more and 100% by mass or less of the dispersing agent dissolved at the time of forming the fine particles is embedded in the fine particles. A method for producing fine particles of a water-insoluble compound.
The polymer dispersant is characterized in that the dispersant is a polymer dispersant having a structural portion showing an interaction attracting the water-insoluble compound composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group. Item 20. The method for producing fine particles according to Item 20.
In producing a fine particle of the water-insoluble compound in which a solution in which a water-insoluble compound is dissolved in a good solvent and a poor solvent are mixed to embed a dispersant, (i) the dispersion on the good solvent side and / or the poor solvent side Or (ii) preparing a solution in which a dispersant is dissolved in a good solvent separately from these and mixing together with both of the above-mentioned dispersants. A method for producing fine particles of a water-insoluble compound, wherein 80% by mass or more is unevenly distributed in an outer region from the particle surface of the fine particles to 50% of the particle radius.
The dispersant is composed of an aromatic ring and a nitrogen-containing cyclic hydrocarbon group and / or a quaternary ammonium group, and exhibits a mutual interaction that attracts the water-insoluble compound, and the water-insoluble compound is dispersed in a dispersion medium. 23. The polymer dispersant having a steric repulsive portion having a repeating unit containing at least one type of bond selected from an ester bond, an ether bond, and an amide bond. Method for producing fine particles.