JP2015189950A - Coloring material dispersion liquid and production method of the same, resist composition, color filter, liquid crystal display device, and organic light-emitting display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring material dispersion liquid having excellent dispersibility and dispersion stability of a coloring material, from which a coating film with a high contrast can be formed.SOLUTION: The coloring material dispersion liquid comprises (A) a dispersant, (B) a coloring material, and (C) a solvent. The (A) dispersant is a polymer having a structural unit represented by general formula (I) below; and the polymer has a salt formed by at least a part of amino groups included in the structural unit represented by general formula (I) and by a halogenated hydrocarbon that has at least one functional group selected from an acid group and its ester group and may include a hetero atom. Symbols in general formula (I) are described in the specification of the present invention.

Description

  The present invention relates to a color material dispersion and a method for producing the same, a resist composition, a color filter, a liquid crystal display device, and an organic light emitting display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (cell phones, smartphones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.
Under such circumstances, demands for higher luminance, higher contrast, and improved color reproducibility are increasing in color filters.

  Here, the color filter is generally formed on a transparent substrate, a transparent layer formed on the transparent substrate, and composed of a colored layer of three primary colors of red, green, and blue, and on the transparent substrate so as to partition each colored pattern. And a light shielding portion formed.

As a method for forming pixels in a color filter, among others, a pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like.
In a color filter having pixels formed by using a pigment dispersion method, miniaturization of pigments is being studied in order to achieve high brightness and high contrast. By making the pigment finer, it is considered that the scattering of light transmitted through the color filter by the pigment particles is reduced, and high brightness and high contrast are achieved.
However, since the refined pigment particles tend to aggregate, there is a problem that the dispersibility and dispersion stability are lowered.

As a technique for improving the dispersibility and dispersion stability of a finely divided pigment, for example, Patent Document 1 has a specific structural unit having an amino group as a pigment dispersant, and the amino group and a specific A negative resist composition for color filters using a block copolymer in which a salt is formed with an organic acid compound is disclosed.
In Patent Document 2, as a method for producing a pigment dispersion having excellent pigment dispersion stability and high productivity, a pigment, a specific polymer having an amine, a low-molecular compound capable of reacting with the amine, and a solvent are disclosed. A method for producing a pigment dispersion is disclosed in which the pigment is dispersed while mixing and reacting the polymer and the low molecular weight compound.

  In addition, in Patent Document 3, the present inventors have disclosed a pigment, a pigment dispersant, and a curable resin composition for a color filter that are excellent in pigment dispersion stability, suppressed in contrast, and excellent in alkali developability. A color filter curable resin composition comprising a photopolymerizable polyfunctional compound, a photopolymerization initiator, a borate ester compound and / or a boronic acid compound, an alkali-soluble resin, and a solvent is disclosed. Yes.

JP 2010-237571 A JP 2010-235748 A JP 2013-029832 A

Due to the demand for further thinning of the display device, the demand for further thinning of the color filter is also increasing. In order to further reduce the film thickness while satisfying the requirement of color reproducibility, it is necessary to increase the concentration of the color material in the resin composition for pixel formation.
However, in order to increase the color material concentration in the resin composition, it is necessary to increase the amount of the dispersant, which causes problems such as generation of a development residue and a delay in development time.

  The present invention has been made in view of the above circumstances, and is excellent in dispersibility and dispersion stability of a color material, and can be used to form a high-contrast coating film. Resist composition capable of forming a high-contrast colored layer with suppressed development and generation stability, and high-contrast optical performance with the resist composition. It is an object of the present invention to provide a color filter, a liquid crystal display device having excellent display characteristics by using the color filter, and an organic light emitting display device.

  The colorant dispersion according to the present invention is a colorant dispersion containing (A) a dispersant, (B) a colorant, and (C) a solvent, wherein (A) the dispersant is represented by the following general formula: A polymer having a structural unit represented by (I), which is selected from the group consisting of at least part of an amino group of the structural unit represented by general formula (I), an acidic group and an ester group thereof. It is a polymer formed by salt formation with a halogenated hydrocarbon having one or more kinds of functional groups and optionally having a hetero atom.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ａは、直接結合又は２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２とＲ^３とが互いに結合して環構造を形成してもよい。Ｒ^２及びＲ^３は、互いに同一であっても異なっていてもよい。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, and R ² and R ³ each independently contain a hydrogen atom or a hetero atom. Represents a good hydrocarbon group, and R ² and R ³ may be bonded to each other to form a ring structure, and R ² and R ³ may be the same or different from each other.

A first method for producing a color material dispersion according to the present invention is a method for producing a color material dispersion containing (A) a dispersant, (B) a color material, and (C) a solvent,
A halogen having a hetero atom having a polymer having a structural unit represented by the following general formula (I), one or more functional groups selected from the group consisting of an acidic group and an ester group thereof One or more functional groups selected from the group consisting of at least a part of the amino group of the structural unit represented by the general formula (I) and the acidic group and ester group thereof And (A) preparing a dispersant by salt formation with a halogenated hydrocarbon which may have a hetero atom,
(C) in the presence of the dispersant (A) in a solvent, and (B) a step of dispersing the coloring material.

A second method for producing a color material dispersion according to the present invention is a method for producing a color material dispersion containing (A) a dispersant, (B) a color material, and (C) a solvent,
(C) a solvent, a polymer having a structural unit represented by the following general formula (I), and one or more functional groups selected from the group consisting of an acidic group and an ester group thereof, and a heteroatom Mixing the halogenated hydrocarbon which may have and (B) the coloring material, at least a part of the amino group of the structural unit represented by the general formula (I), the acidic group and its ester group And (B) a step of dispersing the coloring material while forming a salt with a halogenated hydrocarbon which has one or more functional groups selected from the group consisting of and may have a hetero atom. And

  In the color material dispersion of the present invention and the method for producing the color material dispersion, the color material dispersion has one or more functional groups selected from the group consisting of the acidic group and its ester group, and has a hetero atom. A good halogenated hydrocarbon preferably has an aromatic ring from the viewpoint of the dispersibility and dispersion stability of the coloring material.

  In the color material dispersion of the present invention and the method for producing the color material dispersion, the color material dispersion has one or more functional groups selected from the group consisting of the acidic group and its ester group, and has a hetero atom. The acidic group in a good halogenated hydrocarbon is preferably a carboxyl group from the viewpoint of colorant dispersion stability, alkali developability, and suppression of development residue.

  The resist composition according to the present invention comprises the colorant dispersion according to the present invention, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. To do.

  The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers cures the resist composition according to the present invention. It is characterized by being a colored layer formed.

The present invention provides a liquid crystal display device comprising the color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
The present invention also provides an organic light emitting display device comprising the color filter according to the present invention and an organic light emitter.

  According to the present invention, the colorant dispersion is excellent in dispersibility and dispersion stability of the colorant, and can be used to form a high-contrast coating film, and its manufacturing method, the dispersibility and dispersion stability of the colorant, and A resist composition capable of forming a high-contrast colored layer in which development residue is suppressed, a color filter formed using the resist composition and having high optical performance with excellent contrast, and the color filter By using it, a liquid crystal display device excellent in display characteristics and an organic light emitting display device can be provided.

FIG. 1 is a schematic view showing an example of the color filter of the present invention. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention.

Hereinafter, the color material dispersion according to the present invention, the manufacturing method thereof, the resist composition, the color filter, the liquid crystal display device, and the organic light emitting display device will be described in detail in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.
In the present invention, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
In the present invention, the organic group means a group having one or more carbon atoms.

[Colorant dispersion]
The colorant dispersion according to the present invention is a colorant dispersion containing (A) a dispersant, (B) a colorant, and (C) a solvent, wherein (A) the dispersant is represented by the following general formula: A polymer having a structural unit represented by (I), which is selected from the group consisting of at least part of an amino group of the structural unit represented by general formula (I), an acidic group and an ester group thereof. A halogenated hydrocarbon having one or more functional groups and optionally having a heteroatom (hereinafter sometimes referred to as a specific halogenated hydrocarbon. Also, from the group consisting of an acidic group and an ester group thereof) One or more selected functional groups may be simply referred to as “acidic group etc.”) and are a salt-formed polymer.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基、Ａは、直接結合又は２価の連結基、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^２とＲ^３とが互いに結合して環構造を形成してもよい。Ｒ^２及びＲ^３は、互いに同一であっても異なっていてもよい。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, and R ² and R ³ each independently contain a hydrogen atom or a hetero atom. Represents a good hydrocarbon group, and R ² and R ³ may be bonded to each other to form a ring structure, and R ² and R ³ may be the same or different from each other.

  In the colorant dispersion of the present invention, (A) as a dispersant, at least a part of the amino group of the polymer having the structural unit represented by the general formula (I) and a specific halogenated hydrocarbon form a salt. Since the polymer thus used is used, it is possible to form a coating film having excellent dispersibility and dispersion stability of the color material and high contrast. In addition, the resist composition prepared using the color material dispersion can shorten the development time during alkali development while suppressing the occurrence of development residues.

The use of the above-mentioned polymer salted with the specific halogenated hydrocarbon as a dispersing agent has the following effect, but is estimated as follows.
Conventionally, it is possible to improve dispersibility, dispersion stability, and alkali developability by using a copolymer having an amino group in which a salt of the amino group and an organic acid compound is formed as a dispersant. It was known (for example, Patent Document 1).
However, the technique disclosed in Patent Document 1 has insufficient dispersion stability particularly when a fine color material is dispersed. When the amino group of the copolymer and the acidic group of the organic acid compound form a salt, the salt is likely to dissociate, and as a result, it is estimated that the dispersion stability decreases. Further, since the salt is formed by acid-base interaction, when the alkali developer comes into contact, the dissociated organic acid compound re-forms a salt with the alkali component in the developer, and is removed from the copolymer. Estimated to separate. Since the copolymer from which the organic acid compound was eliminated decreased in alkali solubility, it was presumed that it remained on the substrate together with the pigment to form a residue.
On the other hand, in the copolymer having an amino group, the dispersion stability is improved when a salt formed by the amino group of the copolymer and a halogenated hydrocarbon is used as a dispersant. I got the knowledge. As a result of intensive studies, the present inventors have found that when the amino group of the copolymer and the halogenated hydrocarbon are salt-formed, the halogenated hydrocarbon is almost eliminated from the copolymer even when an alkaline developer is used. It became clear not to release. However, when a salt is formed using a halogenated hydrocarbon, the polarity of the amino group increases. For this reason, the interaction with the base material becomes strong, and it remains on the base material together with the pigment, thereby increasing the generation of residues.

As a result of further studies, the present inventors have found that the polymer has a structural unit represented by the above general formula (I), and includes at least a part of an amino group, a acidic group, and an ester thereof. Dispersibility and dispersion stability by using, as a dispersant, a polymer that has at least one functional group selected from the group consisting of a group and a salt formed with a halogenated hydrocarbon that may have a hetero atom It was found that the development of resist residues in the resist composition is suppressed. When the specific halogenated hydrocarbon is used as an amino group modifier, both the acidic group equivalent side and halogen atom side hydrocarbon of the compound can form a salt with the amino group. However, when an amino group and an acidic group possessed by the specific halogenated hydrocarbon form a salt, the salt is easily dissociated, and finally the amino group and the halogen atom-side hydrocarbon of the compound are stabilized. This is presumed to form a salt. And it is estimated that a dispersibility and dispersion stability improve because a coloring material adsorb | sucks to the salt formation site | part which exists stably. Moreover, since the said specific halogenated hydrocarbon has an acidic group etc., the said dispersing agent is excellent in alkali developability. In particular, since there are acidic groups of the above-mentioned specific halogenated hydrocarbons at the salt forming site where the coloring material is stably adsorbed, it becomes easy to flow while the coloring material is adsorbed to the dissolving dispersant during alkali development. It is presumed that the coloring material is not left on the substrate and the generation of the residue is suppressed.
From the above, the color material dispersion of the present invention is excellent in dispersibility and dispersion stability of the color material, can form a high-contrast coating film, and is prepared using the color material dispersion. The resist composition suppresses generation of development residues and is excellent in alkali developability.

The color material dispersion of the present invention contains at least (A) a dispersant, (B) a color material, and (C) a solvent, and further contains other components as long as the effects of the present invention are not impaired. It may contain.
Hereinafter, each component of the color material dispersion of the present invention will be described in detail in order.

<(A) Dispersant>
In the present invention, (A) the dispersant is a polymer having a structural unit represented by the following general formula (I), and at least one of the amino groups of the structural unit represented by the general formula (I). And a halogenated hydrocarbon which has one or more functional groups selected from the group consisting of an acidic group and an ester group thereof, and may have a hetero atom (hereinafter referred to as salt type) May be referred to as a polymer).
The structural unit represented by the following general formula (I) has basicity and functions as an adsorption site for the coloring material.

（一般式（Ｉ）中の各符号は、上述のとおりである。）

(The symbols in general formula (I) are as described above.)

(Polymer having structural unit represented by general formula (I))
The colorant dispersion of the present invention uses a polymer in which at least a part of the polymer having the structural unit represented by the general formula (I) is salted with a specific halogenated hydrocarbon described later. The adsorption performance to the colorant is improved, and the dispersibility and dispersion stability of the color material are improved.

In general formula (I), A is a direct bond or a divalent linking group. The direct bond means that A does not have an atom, that is, C (carbon atom) and N (nitrogen atom) in the general formula (I) are bonded without interposing another atom. To do.
Examples of the divalent linking group in A include an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R'-OR “-: R ′ and R” are each independently an alkylene group), combinations thereof, and the like.
Among these, from the viewpoint of dispersibility, A in the general formula (I) is preferably a direct bond, a -CONH- group, or a divalent linking group containing a -COO- group.

Examples of the hydrocarbon group in the hydrocarbon group that may include a hetero atom in R ² and R ³ include an alkyl group, an aralkyl group, and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the like. 1-18 are preferable and, among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. 7-20 are preferable and, as for the carbon atom number of an aralkyl group, 7-14 are more preferable.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. 6-24 are preferable and, as for the carbon atom number of an aryl group, 6-12 are more preferable. The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.
The hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
Moreover, the hydrogen atom in a hydrocarbon group may be substituted by halogen atoms, such as a C1-C5 alkyl group, a fluorine atom, a chlorine atom, and a bromine atom.

The phrase “R ² and R ³ are bonded to each other to form a ring structure” means that R ² and R ³ form a ring structure through a nitrogen atom. The ring structure is not particularly limited, and examples thereof include a pyridine ring, a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, among them, R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ are bonded to form a pyridine ring, a pyrrolidine ring, It is preferable to form a piperidine ring or a morpholine ring.

Examples of the structural unit represented by the general formula (I) include nitrogen-containing (meth ) Acrylate and the like, but not limited thereto.
The structural unit represented by the general formula (I) may be composed of one type or may include two or more types of structural units.

The polymer having the structural unit represented by the general formula (I) preferably further includes a portion having solvent affinity from the viewpoint of improving dispersibility. As the solvent affinity site, a monomer having an ethylenically unsaturated bond that can be polymerized with a monomer that derives the structural unit represented by the general formula (I) is selected depending on the solvent so as to have solvent affinity. It is preferable to select and use as appropriate. As a standard, it is preferable to introduce a solvent-affinity site so that the solubility of the polymer at 23 ° C. is 50 (g / 100 g solvent) or more with respect to the solvent used in combination.
As the polymer used in the present invention, the dispersibility and dispersion stability of the coloring material and the heat resistance of the resin composition can be improved, and a high-luminance and high-contrast colored layer can be formed. A basic block copolymer having a structure and a basic graft copolymer having a specific structure described later are preferable, and the basic block copolymer is particularly preferable.
Hereinafter, preferable basic block copolymers and basic graft copolymers will be described in order.

1. Basic Block Copolymer As a basic block copolymer preferably used in the present invention, a basic block portion having a structural unit represented by the general formula (I) (hereinafter, referred to as A block may be described). And a solvent-affinity block part (hereinafter referred to as B block) that does not have the structural unit represented by the general formula (I) and has a structural unit copolymerizable with the general formula (I). And a basic block copolymer. In the present invention, the arrangement of each block of the basic block copolymer is not particularly limited, and for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer and the like can be used. Among these, an AB block copolymer or an ABA block copolymer is preferable in terms of excellent dispersibility.

  The method for producing the basic block copolymer is not particularly limited. Although a block copolymer can be produced by a known method, it is preferable to produce it by a living polymerization method. This is because chain transfer and deactivation are unlikely to occur, a copolymer having a uniform molecular weight can be produced, and dispersibility and the like can be improved. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a group transfer polymerization method, and a living cation polymerization method. A copolymer can be produced by sequentially polymerizing monomers by these methods. For example, a basic block copolymer can be produced by first producing the A block and polymerizing the structural units constituting the B block into the A block. In the above production method, the order of polymerization of the A block and the B block can be reversed. Also, the A block and the B block can be manufactured separately, and then the A block and the B block can be coupled.

(1) Basic block portion (A block) having a structural unit represented by general formula (I)
The basic block copolymer has a basic block portion having a structural unit represented by the general formula (I). In addition, since the structural unit represented by general formula (I) is as above-mentioned, description here is abbreviate | omitted.
In the basic block portion having the structural unit represented by the general formula (I), it is preferable that three or more structural units represented by the general formula (I) are included. Among these, from the viewpoint of improving dispersibility and dispersion stability, it is preferably 3 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

The basic block part may have a structural unit other than the structural unit represented by the general formula (I) as long as the object of the present invention is achieved, and the structural unit represented by the general formula (I) Any structural unit copolymerizable with can be contained. For example, examples of the structural unit other than the structural unit represented by the general formula (I) that may be contained in the basic block part include a structural unit represented by the general formula (II) described later.
In the basic block part, the content ratio of the structural unit represented by the general formula (I) is preferably 50 to 100% by mass when the total structural unit of the basic block part is 100% by mass, More preferably, it is 80-100 mass%, and it is most preferable that it is 100 mass%. The higher the proportion of the structural unit represented by the general formula (I), the better the adsorptive power to the coloring material, and the better the dispersibility and dispersion stability of the basic block copolymer. is there. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the basic block part which has a structural unit represented by general formula (I).

In the basic block copolymer, the content of the structural unit represented by the general formula (I) is such that all the structural units of the basic block copolymer are excellent in terms of dispersibility and dispersion stability. When it is 100 mass%, it is preferable that it is 5-60 mass%, and it is more preferable that it is 10-50 mass%. In addition, the content rate of the said structural unit is computed from the preparation mass at the time of synthesize | combining the basic block copolymer which has a structural unit represented by general formula (I).
The structural unit represented by the general formula (I) is only required to have an affinity with the color material, and may be composed of one kind or may contain two or more kinds of structural units.

(2) Solvent affinity block part (B block) which does not have a structural unit represented by the said general formula (I), but has a structural unit copolymerizable with general formula (I)
The basic block copolymer does not have the structural unit represented by the general formula (I) but has a solvent affinity block portion having a structural unit copolymerizable with the general formula (I). By having the said block part, solvent affinity is made more favorable and the dispersibility and dispersion stability of a coloring material are improved.

  Examples of the structural unit constituting the solvent affinity block (B block) include monomers having an ethylenically unsaturated double bond, and among them, the structural unit represented by the following general formula (II) is preferable. .

（一般式（ＩＩ）中、Ａ’は、直接結合又は２価の連結基、Ｒ^４は、水素原子又はメチル基、Ｒ^５は、炭化水素基、−［ＣＨ（Ｒ^６）−ＣＨ（Ｒ^７）−Ｏ］_ｘ−Ｒ^８又は−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^８で示される１価の基である。Ｒ^６及びＲ^７は、それぞれ独立に水素原子又はメチル基であり、Ｒ^８は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ、又は−ＣＨ_２ＣＯＯＲ^９で示される１価の基であり、Ｒ^９は水素原子又は炭素原子数１〜５のアルキル基である。
上記炭化水素基は、置換基を有していてもよい。
ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In General Formula (II), A ′ is a direct bond or a divalent linking group, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ is a monovalent group, and R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group. R ⁸ is a hydrogen atom, a hydrocarbon group, a monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , and R ⁹ is a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. It is an alkyl group.
The hydrocarbon group may have a substituent.
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

  In the general formula (II), A ′ can be the same as A in the general formula (I). Among these, a divalent linking group containing a direct bond, a —CONH— group, or a —COO— group is preferable from the viewpoint of solubility in an organic solvent.

In the general formula (II), R ⁵ is a hydrocarbon group, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ^8. Indicates.
The hydrocarbon group for R ⁵ is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, 2 -Ethylhexyl group, 2-ethoxyethyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like can be mentioned.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that there is a double bond at the terminal of the alkenyl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group, and may further have a substituent. 6-24 are preferable and, as for the carbon atom number of an aryl group, 6-12 are more preferable.
Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, Furthermore, you may have a substituent. 7-20 are preferable and, as for the carbon atom number of an aralkyl group, 7-14 are more preferable.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

In the above R ⁵ , x is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2, and y is an integer of 1-5, preferably an integer of 1-4, more preferably. Is 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

The hydrocarbon group for R ⁸ can be the same as that shown for R ⁵ .
R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be linear, branched, or cyclic.
Moreover, R ⁵ in the structural unit represented by the general formula (II) may be the same or different from each other.

As the R ⁵ , it is preferable to use one having excellent solubility with a solvent described later. Specifically, for example, the solvent is an ether alcohol generally used as a solvent for a resist composition. In the case of using a solvent such as acetate, ether, or ester, a methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, or the like is preferable.

Further, the R ⁵ is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as the dispersion performance of the basic block copolymer is not hindered. Alternatively, after the synthesis of the basic block copolymer, the substituent may be added by reacting with the compound having the substituent.

  The number of structural units constituting the solvent affinity block (B block) is not particularly limited, but the solvent affinity site and the color material affinity site effectively act to improve the dispersibility of the color material. The number is preferably 10 to 300, more preferably 10 to 100, and still more preferably 10 to 70.

In the basic block copolymer, the content of the structural unit represented by the general formula (II) is 40 to 95% by mass when all the structural units of the basic block copolymer are 100% by mass. It is preferably 60 to 90% by mass.
In addition, the content rate of the said structural unit is computed from the preparation amount at the time of synthesize | combining the block part which has a structural unit represented by general formula (II).

  The solvent affinity block part (B block) may be appropriately selected from structural units so as to function as a solvent affinity site, and the structural unit may be composed of one type or two or more types of configuration. Units may be included. When two or more structural units are included, two or more structural units may be randomly arranged in the block portion.

  In the basic block copolymer, the ratio m / n of the unit number m of the structural unit of the basic block part (A block) and the unit number n of the structural unit of the solvent affinity block part (B block) Is preferably in the range of 0.05 to 1.5, and more preferably in the range of 0.1 to 1.0 from the viewpoint of dispersibility and dispersion stability of the coloring material.

The mass average molecular weight Mw of the basic block copolymer is not particularly limited, but is preferably 1000 to 20000 from the viewpoint of improving the dispersibility and dispersion stability of the coloring material, and is 2000 to 15000. More preferably, it is more preferably 3000 to 12000.
Here, the weight average molecular weight is determined as a standard polystyrene conversion value by (Mw) and gel permeation chromatography (GPC).
In the present invention, the mass average molecular weight Mw of the basic block copolymer is determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and the polystyrene standard for calibration curve was Mw377400, 210500, 96000, 50400. , 20650, 10850, 5460, 2930, 1300, 580 (Easy PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

The amine value of the basic block copolymer is not particularly limited, but from the viewpoint of dispersibility and dispersion stability of the color material, the lower limit is preferably 20 mgKOH / g or more, and 30 mgKOH / g or more. Is more preferable, and it is still more preferable that it is 40 mgKOH / g or more. Moreover, as an upper limit, it is preferable that it is 180 mgKOH / g or less, It is more preferable that it is 160 mgKOH / g or less, It is still more preferable that it is 150 mgKOH / g or less. If it is more than the said lower limit, dispersion stability is more excellent. Moreover, if it is below the said upper limit, it is excellent in compatibility with another component and can form a more uniform coating film.
In the present invention, the amine value means the mass (mg) of potassium hydroxide equivalent to the amount of hydrochloric acid necessary for neutralizing 1 g of the solid content of the resin, and the method described in JIS K 7237 is used. It is a value measured by a similar method.

The acid value of the basic block copolymer is not particularly limited, but is preferably 25 mgKOH / g or less, more preferably 15 mgKOH / g or less, and 0 mgKOH from the viewpoint of excellent solvent resolubility. / G is particularly preferable.
In the present invention, the solvent re-solubility means ease of dissolution of the dried solidified product of the photosensitive colored resin composition in a solvent (usually a solvent contained in the photosensitive colored resin composition). When the photosensitive colored resin composition adheres to the tip of the die lip when coating with a die coater, a solidified product is generated by drying. If the solidified product is not easily dissolved in the photosensitive colored resin composition when coating is resumed, the solidified product on the die lip is partly peeled off and easily adheres to the color filter colored layer, resulting in foreign matter defects. .
Further, in the present invention, the acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample (solid content of the resin), and the method described in JIS K 0070 It is a value measured by a similar method.

2. Basic Graft Copolymer The basic graft copolymer preferably used in the present invention has a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (III). Examples include basic graft copolymers.

（一般式（ＩＩＩ）中、Ｒ^１０は、水素原子又はメチル基、Ｌは、直接結合又は２価の連結基、Ｐｏｌｙｍｅｒは、下記一般式（ＩＶ）又は下記一般式（Ｖ）で表される構成単位を少なくとも１種有するポリマー鎖を表す。）

(In general formula (III), R ¹⁰ is a hydrogen atom or a methyl group, L is a direct bond or a divalent linking group, and Polymer is represented by the following general formula (IV) or the following general formula (V). (Represents a polymer chain having at least one structural unit.)

（一般式（ＩＶ）及び一般式（Ｖ）中、Ｒ^１１は水素原子又はメチル基であり、Ｒ^１２は炭化水素基、シアノ基、−［ＣＨ（Ｒ^１３）−ＣＨ（Ｒ^１４）−Ｏ］_ｘ−Ｒ^１５、−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^１５、−［ＣＯ−（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^１５、−ＣＯ−Ｏ−Ｒ^１６又は−Ｏ−ＣＯ−Ｒ^１７で示される１価の基である。Ｒ^１３及びＲ^１４は、それぞれ独立に水素原子又はメチル基である。
Ｒ^１５は、水素原子、炭化水素基、−ＣＨＯ、−ＣＨ_２ＣＨＯ又は−ＣＨ_２ＣＯＯＲ^１８で示される１価の基であり、Ｒ^１６は、炭化水素基、シアノ基、−［ＣＨ（Ｒ^１３）−ＣＨ（Ｒ^１４）−Ｏ］_ｘ−Ｒ^１５、−［（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^１５、−［ＣＯ−（ＣＨ_２）_ｙ−Ｏ］_ｚ−Ｒ^１５で示される１価の基である。Ｒ^１７は炭素原子数１〜１８のアルキル基であり、Ｒ^１８は水素原子又は炭素原子数１〜５のアルキル基を示す。
上記炭化水素基は、置換基を有していてもよい。
ｍは１〜５の整数、ｎ及びｎ’は５〜２００の整数を示す。ｘは１〜１８の整数、ｙは１〜５の整数、ｚは１〜１８の整数を示す。）

(In General Formula (IV) and General Formula (V), R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydrocarbon group, a cyano group, — [CH (R ¹³ ) —CH (R ¹⁴ ) —O. _{^{] x -R 15, - [(}} CH 2) y -O] z -R 15, - [CO- (CH 2) y -O] z -R 15, -CO-O-R 16 or -O-CO A monovalent group represented by -R ^17. R ¹³ and R ¹⁴ each independently represents a hydrogen atom or a methyl group;
R ¹⁵ is a monovalent group represented by a hydrogen atom, a hydrocarbon group, —CHO, —CH ₂ CHO or —CH ₂ COOR ¹⁸ , and R ¹⁶ is a hydrocarbon group, a cyano group, — [CH (R ¹³ ) —CH (R ¹⁴ ) —O] _x —R ¹⁵ , — [(CH ₂ ) _y —O] _z —R ¹⁵ , — [CO— (CH ₂ ) _y —O] _z —R ^15. It is a monovalent group. R ¹⁷ is an alkyl group having 1 to 18 carbon atoms, and R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The hydrocarbon group may have a substituent.
m represents an integer of 1 to 5, and n and n ′ represent an integer of 5 to 200. x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )

(1) Constituent Unit Represented by General Formula (III) The basic graft copolymer has a constitutional unit represented by the general formula (III) containing a polymer chain in the side chain. Will be better.
In the general formula (III), L is a direct bond or a divalent linking group. The divalent linking group in L is not particularly limited as long as it can link an ethylenically unsaturated double bond and a polymer chain. Examples of the divalent linking group in L include an alkylene group, an alkylene group having a hydroxyl group, an arylene group, a —CONH— group, a —COO— group, a —NHCOO— group, an ether group (—O— group), and a thioether group. (—S— group), and combinations thereof. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when -CONH- is contained in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the polymer chain side of the side chain. On the carbon atom side, -CO may be a polymer chain side chain.

The hydrocarbon group in R ¹² , R ¹⁵ , and R ¹⁶ can be the same as that shown for R ⁵ . The alkyl group having 1 to 18 carbon atoms in R ¹⁷ may be similar to that shown by the R ^5. The alkyl group having 1 to 5 carbon atoms in R ¹⁸ may be similar to that shown by the R ^9.
In R ¹² and R ¹⁶ , x, y and z can be the same as those shown for R ⁵ .

  The polymer chain contained in the structural unit represented by the general formula (III) (which may be simply referred to as “Polymer”) includes methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (among the above structural units). (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Those having a structural unit derived from (meth) acrylate, phenyl (meth) acrylate, styrene, α-methylstyrene, vinylcyclohexane and the like are preferable. However, it is not limited to these.

  In general formula (V), m is an integer of 1-5, Preferably it is an integer of 2-5, More preferably, it is an integer of 4 or 5. The number of units n and n ′ of the polymer chain constituent units may be an integer of 5 to 200, and is not particularly limited, but is preferably in the range of 5 to 100.

The mass average molecular weight Mw of the polymer chain in Polymer is preferably in the range of 500 to 20000, and more preferably in the range of 1000 to 10,000. By being the said range, while being able to hold | maintain sufficient steric repulsion effect as a dispersing agent, the increase in the time required for dispersion | distribution of the color material by a steric effect can also be suppressed.
In addition, the mass average molecular weight Mw of the polymer chain in Polymer is measured by GPC in the same manner as the above-mentioned basic block copolymer.

Further, as a guide, the polymer chain in Polymer preferably has a solubility at 23 ° C. of 50 (g / 100 g solvent) or more with respect to the solvent used in combination.
The solubility of the polymer chain can be based on the solubility of the raw material into which the polymer chain is introduced when preparing the basic graft copolymer. For example, when a polymerizable oligomer containing a polymer chain and a group having an ethylenically unsaturated double bond at its end is used to introduce a polymer chain into the basic graft copolymer, the polymerizable oligomer has the above solubility. If you have. In addition, after a copolymer is formed with a monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer is used. In the case of introducing a polymer chain, it is sufficient that the polymer chain containing the reactive group has the above-described solubility.

  The polymer chain may be a homopolymer or a copolymer. Moreover, the polymer chain contained in the structural unit represented by the general formula (III) may be used alone or in combination of two or more in the basic graft copolymer.

In the basic graft copolymer, the ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (III) is not particularly limited, but is 3:97 by mass ratio. -80: 20 is preferable, 5: 95-60: 40 is more preferable, and 10: 90-50: 50 is further more preferable. If it is within the above range, the ratio of the basic site and the solvent affinity site in the basic graft copolymer is appropriate, the solubility in the solvent and the adsorptivity to the coloring material are good, the excellent dispersibility, and Dispersion stability is obtained. Note that the ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (III) is the same as that used in the synthesis of the basic graft copolymer. Calculated from mass.

The mass average molecular weight Mw of the basic graft copolymer is preferably in the range of 1000 to 100,000, more preferably in the range of 3000 to 30000, and in the range of 5000 to 20000. Is more preferable. By being in the above range, the color material can be uniformly dispersed.
In addition, the mass average molecular weight Mw of a basic graft copolymer is measured by GPC by the method similar to the above-mentioned basic block copolymer.

  The basic graft copolymer used for the basic graft copolymer before forming a salt having the structural unit represented by the general formula (I) and the structural unit represented by the following general formula (III): Although it does not specifically limit as a manufacturing method of a polymer, For example, the nitrogen-containing monomer represented by the following general formula (I '), and the structural unit represented by the said general formula (IV) or the said general formula (V) And a copolymerization method containing a macromonomer composed of a polymer chain having at least one of the above and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component. Further, other monomers can be used as necessary, and a known polymerization means can be used as the polymerization means.

（一般式（Ｉ’）中、Ｒ^１〜Ｒ^３、及びＡは、一般式（Ｉ）と同様である。）

(In General Formula (I ′), R ^{1 to} R ³ and A are the same as those in General Formula (I).)

In addition, after a copolymer is formed by addition polymerization of the monomer represented by the general formula (I ′) and another monomer containing a group having an ethylenically unsaturated double bond, You may introduce | transduce a polymer chain using the polymer chain containing the reactive group which can react with the reactive group contained. Specifically, for example, a polymer containing a functional group that reacts with a substituent after synthesizing a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group. The polymer chain may be introduced by reacting with a chain.
For example, a polymer chain having a glycidyl group at the terminal is reacted with a copolymer having a carboxyl group at the side chain, or a polymer chain having a hydroxy group at the terminal is reacted with a copolymer having an isocyanate group at the side chain. Alternatively, polymer chains can be introduced.
In the above polymerization, additives generally used in the polymerization, for example, a polymerization initiator, a dispersion stabilizer, a chain transfer agent and the like may be used.

  The amine value of the basic graft copolymer is not particularly limited, but from the viewpoint of dispersibility and dispersion stability of the color material, the lower limit is preferably 20 mgKOH / g or more, and 30 mgKOH / g or more. Is more preferable, and it is still more preferable that it is 40 mgKOH / g or more. Moreover, as an upper limit, it is preferable that it is 180 mgKOH / g or less, It is more preferable that it is 160 mgKOH / g or less, It is still more preferable that it is 150 mgKOH / g or less. If it is more than the said lower limit, dispersion stability is more excellent. Moreover, if it is below the said upper limit, it is excellent in compatibility with another component and can form a more uniform coating film.

  The acid value of the basic graft copolymer is not particularly limited, but the acid value is 25 mgKOH / g or less from the viewpoint of excellent solvent resolubility and resist pattern peeling during development. Preferably, it is 15 mgKOH / g or less, more preferably 0 mgKOH / g.

(Halogenated hydrocarbon having at least one functional group selected from the group consisting of an acidic group and its ester group, and optionally having a hetero atom)
In the present invention, the modifying agent that forms a salt with at least a part of the amino group of the polymer having the structural unit represented by the general formula (I) is selected from the group consisting of an acidic group and an ester group thereof. Halogenated hydrocarbons having one or more functional groups and optionally having heteroatoms are used. The specific halogenated hydrocarbon forms a salt polymer excellent in dispersibility and dispersion stability by forming a salt with at least a part of the amino group of the polymer. In the present invention, the specific halogenated hydrocarbon is not particularly limited as long as it can react with the amino group of the polymer, and can be appropriately selected from known halogenated hydrocarbons. Examples of the hetero atom that may be contained in the hydrocarbon chain include O (oxygen atom), S (sulfur atom), and N (nitrogen atom).

In the present invention, an acidic group refers to a group that exhibits acidity by releasing protons in water. Specific examples of the acidic group include a carboxy group (—COOH), a sulfo group (—SO ₃ H), a phosphono group (—P (═O) (OH) ₂ ), a phosphinico group (> P (═O) (OH )), Boronic acid groups (—B (OH) ₂ ), borinic acid groups (> BOH) and the like, and may be anions in which hydrogen atoms are dissociated, such as carboxylato groups (—COO ⁻ ). Furthermore, it may be an acid salt that forms a salt with an alkali metal ion such as sodium ion or potassium ion.
Moreover, as an ester group of an acidic group, carboxylic acid ester (—COOR), sulfonic acid ester (—SO ₃ R), phosphoric acid ester (—P (═O) (OR) ₂ ), (> P (═O ) (OR)), boronic acid ester (—B (OR) ₂ ), borinic acid ester (> BOR) and the like. R is a hydrocarbon group and is not particularly limited, but is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group or an ethyl group, from the viewpoint of dispersibility and dispersion stability. More preferred.

  In the present invention, from the viewpoint of dispersibility, dispersion stability, alkali developability, and development residue suppression, the specific halogenated hydrocarbon is a carboxy group, a boronic acid group, a borinic acid group, their anions, and these It preferably has a functional group selected from an alkali metal salt of these and an ester thereof, and more preferably has a functional group selected from a carboxy group, a carboxylate group, a carboxylate group, and a carboxylate ester.

  In the present invention, the specific halogenated hydrocarbon may have two or more functional groups selected from the group consisting of the acidic group and an ester group thereof. In the case of having two or more functional groups, the plural functional groups may be the same or different. In the present invention, the number of the functional groups contained in the specific halogenated hydrocarbon is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

Specific examples of the halogen atom possessed by the specific halogenated hydrocarbon in the present invention include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It is preferably an atom or an iodine atom.
The halogen atom is directly bonded to any carbon atom in the specific halogenated hydrocarbon. For example, it may be directly bonded to the carbon atom constituting the aromatic ring, or may be bonded to the carbon atom constituting the carbon chain. In the present invention, the above-mentioned specific halogenated hydrocarbon easily forms a salt with an amino group, and the adsorption performance to the coloring material is improved. Among them, the halogen atom is bonded to a carbon atom having no π bond (saturated carbon). It is preferable.

  In addition, the structure of the specific halogenated hydrocarbon used in the present invention is not particularly limited, but among them, a compound having an aromatic ring is preferable from the viewpoint of improving dispersion stability and improving contrast. When the specific halogenated hydrocarbon has an aromatic ring, the affinity with the skeleton of the coloring material described later is improved, the dispersibility and dispersion stability of the coloring material are improved, and the contrast is improved. An excellent coloring composition can be obtained.

In the present invention, the specific halogenated hydrocarbon easily forms a salt with an amino group, improves the adsorption performance to the coloring material, has excellent dispersion stability, and can form a high-contrast colored layer. More preferably, the halogen atom is bonded to a saturated carbon atom, and the saturated carbon atom is bonded to an aromatic ring, that is, a compound represented by the following general formula (VI).
Ph-C (R) _2- X (VI)
(In general formula (VI), Ph represents an aromatic group which may have a substituent and may have a hetero atom, and R represents a hydrogen atom, an acidic group or an ester group thereof, or a substituent. And X represents a halogen atom, and a plurality of Rs may be the same or different, provided that in general formula (VI) The compound represented has at least one acidic group or its ester group as a substituent.)

  Examples of the hydrocarbon group for R in the general formula (VI) include a linear, branched or cyclic alkyl group, an aromatic group, or a combination thereof. Examples of the substituent that the hydrocarbon group may have include an acidic group or an ester group thereof.

As the aromatic ring constituting the aromatic group in the general formula (VI), in addition to a benzene ring, condensed polycycles such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl And chain polycyclic such as diphenylmethane, triphenylmethane, stilbene and the like. The chain polycycle may have O, S, and N in the chain skeleton such as diphenyl ether. In addition, the aromatic ring may be an aromatic heterocyclic ring, specifically, a 5-membered heterocyclic ring such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole; pyran, pyrone, pyridine, 6-membered heterocycles such as pyrone, pyridazine, pyrimidine and pyrazine; and condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline and quinoxaline .
Examples of the substituent that the aromatic group may have include an alkyl group having 1 to 5 carbon atoms, an acidic group, or an ester group thereof.

  In the present invention, the molecular weight of the specific halogenated hydrocarbon is not particularly limited, but it is preferably from 50 to 500 in terms of dispersibility, dispersion stability, alkali developability, and development residue suppression. More preferably, it is -400.

  Preferred specific examples of the specific halogenated hydrocarbon include α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid. Chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3- (bromomethyl) phenylboronic acid, and the like. Among these, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, and 4-iodophenylbenzoic acid are more preferable. This is because excellent dispersion stability, high contrast, and a development residue reducing effect can be obtained.

In the dispersant, the content of the halogenated hydrocarbon which has one or more functional groups selected from the group consisting of an acidic group and an ester group thereof, and may have a hetero atom is good dispersibility and The dispersion stability is not particularly limited as long as the dispersion stability is exhibited, but is preferably 0.01 to 1.0 mol with respect to 1 mol equivalent of the amino group of the structural unit represented by the general formula (I). The dispersibility of the coloring material is about equivalent, more preferably 0.03 to 0.8 molar equivalent, more preferably 0.05 to 0.7 molar equivalent, and particularly preferably 0.1 to 0.6 molar equivalent. From the viewpoint of improving dispersion stability, improving alkali developability and development residue suppression.
In addition, the said specific halogenated hydrocarbon may be used individually by 1 type, and may combine 2 or more types. When combining 2 or more types, it is preferable that the total content is in the above range.

In the present invention, other modifiers different from the above-mentioned specific halogenated hydrocarbons may be used in combination as long as the effects of the present invention are not impaired. Other modifiers may be any compound that reacts with a copolymer having an amino group, and conventionally known modifiers can be used.
Specific examples of the modifier include organic acid compounds, halogenated hydrocarbons that do not have an acidic group and an ester group thereof, among others, from the viewpoint of dispersibility and dispersion stability of the coloring material, acidic groups and The halogenated hydrocarbon which does not have the ester group is preferable, The molecular weight is 60-500, Especially, the halogenated hydrocarbon which does not have the acidic group of the molecular weight 90-400 and the ester group is preferable.
Examples of the halogenated hydrocarbon having no acidic group and its ester group include alkyl halide, allyl halide, and halogenated aralkyl.
Examples of the alkyl halide include methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, n-butyl chloride, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride. Etc. Examples of the allyl halide include allyl chloride, allyl bromide, and allyl iodide. Examples of the halogenated aralkyl include benzyl chloride, benzyl bromide, benzyl iodide, naphthylmethyl chloride, pyridylmethyl chloride, naphthylmethyl bromide, and pyridylmethyl bromide.
In the present invention, among these, benzyl halide is more preferable from the viewpoint of improving the dispersion stability of the coloring material and improving the contrast of the colored layer.

  When the specific halogenated hydrocarbon is used in combination with another modifier as the modifier, the total content of the specific halogenated hydrocarbon and the other modifier is represented by the general formula (I). Is preferably about 0.01 to 1.0 molar equivalent, more preferably 0.03 to 0.8 molar equivalent, and more preferably 0.05 to 0.7 relative to 1 molar equivalent of the amino group contained in the structural unit. The molar equivalent, particularly preferably 0.1 to 0.6 molar equivalent, is preferable from the viewpoint of improving the dispersibility and dispersion stability of the coloring material, and improving the alkali developability and the development residue suppression.

A method for preparing a salt copolymer in which at least a part of an amino group of the structural unit of the polymer having the structural unit represented by the general formula (I) and a salt of the specific halogenated hydrocarbon form a salt As a method of adding the above-mentioned specific halogenated hydrocarbon in a solvent for dissolving or dispersing the polymer having the structural unit represented by the above general formula (I) and stirring (heating if necessary). Can be mentioned.
In addition, the amino group which the said structural unit of the polymer which has a structural unit represented by the said general formula (I) has, and the halogen atom side of the said specific halogenated hydrocarbon form the salt, For example, it can be confirmed by a known method such as NMR.

The acid value of the obtained salt-type copolymer is preferably 0 to 90 mgKOH / g, and preferably 0 to 60 mgKOH / g, from the viewpoint of excellent solvent resolubility and resist pattern peeling during development. It is more preferable.
The amine value of the salt-type copolymer is not particularly limited, but from the viewpoint of dispersibility and dispersion stability of the color material, the lower limit is preferably 5 mgKOH / g or more, and preferably 8 mgKOH / g or more. More preferably, it is more preferably 10 mgKOH / g or more. Moreover, as an upper limit, it is preferable that it is 150 mgKOH / g or less, It is more preferable that it is 130 mgKOH / g or less, It is further more preferable that it is 120 mgKOH / g or less. If it is more than the said lower limit, it is excellent in compatibility with another component and can form a more uniform coating film. Moreover, if it is below the said upper limit, dispersion stability is more excellent.

(Other dispersants)
The colorant dispersion of the present invention may be used in combination with other dispersants as long as the effects of the present invention are not impaired. Other dispersants can be appropriately selected from those conventionally used as dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt or (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; polyurethanes; unsaturated polyamides; polysiloxane Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups (Reaction product obtained by reacting with one or more compounds selected from three types of (polyesteramide) compounds), the above-mentioned block-on-block polymer, the above-mentioned graft copolymer, etc. that are not salt-formed Is mentioned.

  When using other dispersants, the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of the dispersant. It is particularly preferred.

<(B) Color material>
In the present invention, the color material is not particularly limited as long as it can produce a desired color when a colored layer of a color filter is formed, and is not particularly limited. In addition to various organic pigments and inorganic pigments, dispersed Possible dyes can be used alone or in admixture of two or more. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of the organic pigment include compounds classified as pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. .) Can be listed with numbers.

C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175;
C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97, C.I. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25; C.I. I. Pigment black 1, C.I. I. Pigment Black 7.

  Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

  For example, when a pattern of a light shielding layer is formed on a color filter substrate as a resist composition to be described later using the color material dispersion of the present invention, a black pigment having a high light shielding property is blended in the ink. As the black pigment having a high light shielding property, for example, an inorganic pigment such as carbon black or iron trioxide or an organic pigment such as cyanine black can be used.

Examples of the dispersible dye include dyes that have been made dispersible by imparting various substituents to the dye, or insolubilized in a solvent using a known rake (chlorination) technique, and solvents having low solubility The dye which became dispersible by using in combination is mentioned. By using such a dispersible dye in combination with the (A) dispersant, the dispersibility and dispersion stability of the dye can be improved.
The dispersible dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guide, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

The average primary particle size of the color material used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a color layer of a color filter, and varies depending on the type of color material used. Is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. When the average primary particle diameter of the color material is in the above range, a display device including a color filter manufactured using the color material dispersion of the present invention can be made with high contrast and high quality. .
In addition, the average particle diameter of the said color material can be calculated | required by the method of measuring the magnitude | size of a primary particle directly from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, for each of 100 or more particles, the volume (mass) of each particle is obtained by approximating a rectangular parallelepiped having the obtained particle size, and is obtained as a volume average particle size, which is defined as the average particle size. Note that the same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

Moreover, although the average dispersed particle diameter of the color material in the color material dispersion varies depending on the type of the color material used, it is preferably within the range of 10 to 100 nm, and more preferably within the range of 15 to 60 nm. preferable.
The average dispersed particle size of the color material in the color material dispersion is the dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. For particle size measurement with a laser light scattering particle size distribution meter, the color material dispersion is appropriately diluted to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrack particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is a volume average particle size.

  The coloring material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Further, a commercially available color material may be used after being refined.

In the color material dispersion of the present invention, the content of the color material is not particularly limited. The content of the color material is 5 to 65 parts by mass, more preferably 8 to 55 parts by mass with respect to 100 parts by mass of the total solid content in the color material dispersion from the viewpoint of dispersibility and dispersion stability. It is preferable to mix.
In the present invention, the solid content is everything other than the solvent described above, and includes monomers dissolved in the solvent.

[(C) Solvent]
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the colorant dispersion and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol, and the like. Carbitol solvents; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, Ester solvents such as n-butyl butyrate, methoxybutyl acetate, ethyl lactate, cyclohexanol acetate; acetone, methyl ethyl ketone, methyl isobutyrate Ketone solvents such as ketone, cyclohexanone, 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, Cellosolve acetate solvents such as ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); Propylene glycol diacetate, 1,3-butylene glycol diacetate, etc. Diacetates; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Ether solvents such as coal dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone Aprotic amide solvents such as lactones; lactone solvents such as γ-butyrolactone; unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbons such as N-heptane, N-hexane and N-octane Solvents: organic solvents such as aromatic hydrocarbons such as toluene and xylene. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether; methyl methoxypropionate and ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate is preferable from the viewpoint of solubility of other components and applicability.

  In the color material dispersion of the present invention, the solvent as described above is usually preferably in the range of 55 to 95% by mass, particularly 65 to 90% by mass with respect to the total amount of the color material dispersion containing the solvent. % Is preferably within the range of 70% to 88% by mass. When there is too little solvent, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve a target chromaticity coordinate.

(Other ingredients)
As long as the effect of this invention is not impaired, you may mix | blend a dispersion auxiliary resin and another component with the coloring material dispersion liquid of this invention as needed.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by a resist composition described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

  The color material dispersion of the present invention is used as a preliminary preparation for preparing a resist composition described later. That is, the color material dispersion is preliminarily prepared in a stage before preparing a resist composition described later, (color material component mass in the composition) / (solid content mass other than the color material component in the composition). This is a colorant dispersion having a high ratio. Specifically, the ratio of (mass of color material component in composition) / (mass of solid content other than color material component in composition) is usually 1.0 or more. By mixing the colorant dispersion and each component described later, the resist composition is excellent in dispersibility and can be prepared.

[Production method of colorant dispersion]
In the present invention, the method for producing the color material dispersion is not particularly limited as long as the (B) color material is a method by which a color material dispersion dispersed in a solvent can be obtained by the salt polymer. Especially, it is preferable to set it as either of the following two manufacturing methods from the point which is excellent in the dispersibility and dispersion stability of a coloring material, and the generation | occurrence | production of the residue of a resist composition is suppressed.

That is, the first method for producing a color material dispersion according to the present invention is a method for producing a color material dispersion containing (A) a dispersant, (B) a color material, and (C) a solvent. ,
Halogen which has a polymer having the structural unit represented by the above general formula (I) and one or more functional groups selected from the group consisting of an acidic group and an ester group thereof, and may have a hetero atom (A) a step of preparing a dispersant by mixing the activated hydrocarbon and salt-forming at least a part of the amino group of the structural unit represented by the general formula (I) with the compound;
(C) in the presence of the dispersant (A) in a solvent, and (B) a step of dispersing the coloring material.

A second method for producing a color material dispersion according to the present invention is a method for producing a color material dispersion containing (A) a dispersant, (B) a color material, and (C) a solvent. ,
(C) a solvent, a polymer having the structural unit represented by the above general formula (I), one or more functional groups selected from the group consisting of an acidic group and an ester group thereof, and a hetero atom. A halogenated hydrocarbon which may be mixed with the colorant (B), and forming at least a part of the amino group of the structural unit represented by the general formula (I) and the compound while forming a salt And (B) a step of dispersing the color material.

According to the first production method, after the salt-type polymer is prepared, the colorant is dispersed using the salt-type polymer as a dispersant. Therefore, the structural unit represented by the general formula (I) is The reaction end point and reaction rate of the polymer having the above-mentioned specific halogenated hydrocarbon can be confirmed accurately.
Further, according to the second production method, since the color material is dispersed while preparing the dispersant of the salt type polymer, the salt type polymer does not self-aggregate, and the color material dispersion is efficiently obtained. It can be prepared and the dispersibility can be improved.

In the first production method and the second production method, the color material can be dispersed using a conventionally known disperser.
Specific examples of the dispersing machine include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 3.0 mm, and more preferably 0.05 to 2.0 mm.

  Specifically, preliminary dispersion is performed with 2.0 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a filter of 0.5 to 2 μm after dispersion.

[Resist composition]
The resist composition according to the present invention comprises the colorant dispersion according to the present invention, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. To do.
The resist composition of the present invention is excellent in the dispersibility and dispersion stability of the color material by using the color material dispersion according to the present invention, and the development time at the time of alkali development while suppressing generation of development residue. Can be shortened.

  The resist composition of the present invention comprises (A) a dispersant, (B) a color material, (C) a solvent, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. In the range which does not impair the effect of this invention, it may contain another component further. Hereinafter, each component contained in the resist composition of the present invention will be described, but (A) the dispersant, (B) the color material, and (C) the solvent are those described in the color material dispersion of the present invention. The description here is omitted.

<(D) Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, acts as a binder resin, and is suitably selected from developers used for pattern formation, particularly preferably those that are soluble in an alkali developer. Can be used.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group as an acidic group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the resist composition.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the resist composition, but also functions as a component that improves the solubility in a solvent and further the solvent re-solubility.

Specific examples of the acrylic copolymer having a carboxyl group include those described in JP 2013-029832 A, and specifically, for example, methyl (meth) acrylate, ethyl (meth) ) A copolymer composed of a monomer having no carboxyl group such as acrylate, and one or more selected from (meth) acrylic acid and anhydrides thereof. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by mass, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

The mass average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 50,000, pattern formation may be difficult during development with an alkaline developer.
In addition, the said mass mean molecular weight (Mw) of the carboxyl group-containing copolymer was measured by Shodex GPC System-21H (polystyrene) as a standard substance and THF as an eluent.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. The epoxy (meth) acrylate resins having a carboxyl group may be used alone or in combination of two or more.

  The alkali-soluble resin used in the resist composition may be used singly or in combination of two or more, and the content is not particularly limited, but the total solid content of the resist composition The alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is more than the above upper limit, the film may be rough during development. Pixel missing may occur. In the present invention, the solid content is everything except the above-mentioned solvent, and includes a liquid polyfunctional monomer.

<(E) polyfunctional monomer>
The polyfunctional monomer used in the resist composition is not particularly limited as long as it can be polymerized by a photoinitiator described later, and usually a compound having two or more ethylenically unsaturated double bonds is used. In particular, a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is preferable.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples thereof include those described in JP2013-029832A.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. When the resist composition of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. Preferred are poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Succinic acid modification of erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa Meth) acrylate are preferable.
The content of the polyfunctional monomer used in the resist composition is not particularly limited, but the polyfunctional monomer is preferably 5 to 60% by mass, more preferably 10 to 40% by mass based on the total solid content of the resist composition. %. If the polyfunctional monomer content is less than the above lower limit, photocuring will not proceed sufficiently, and the exposed part may be eluted during development, and if the polyfunctional monomer content is greater than the above upper limit, alkali developability May decrease.

<(F) Photoinitiator>
There is no restriction | limiting in particular as a photoinitiator used in a resist composition, From the various photoinitiators known conventionally, it can use 1 type or in combination of 2 or more types. Specific examples thereof include those described in JP2013-029832A.

  The content of the photoinitiator used in the resist composition is not particularly limited, but the photoinitiator is preferably 3 to 40% by mass, more preferably 10 to 30% by mass based on the total solid content of the resist composition. Is within the range. If this content is less than the above lower limit, the photocuring will not proceed sufficiently, and the exposed part may be eluted during development, while if it exceeds the above upper limit, the yellowing of the resulting colored layer will become strong and the luminance will be high. May decrease.

<Optional components>
The resist composition may contain various additives as necessary.
Examples of the additive include an antioxidant, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter. Can be mentioned.

  The resist composition of the present invention preferably further contains an antioxidant from the viewpoint of heat resistance. The antioxidant may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include, for example, hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, hydrazine antioxidants, and the like. From the viewpoint, it is preferable to use a hindered phenol-based antioxidant.

  When using antioxidant, the compounding quantity will not be specifically limited if it is a range by which the effect of this invention is not impaired. As a compounding quantity of antioxidant, it is preferable that antioxidant is 0.1-5.0 mass parts with respect to 100 mass parts of total solids in a resist composition, 0.5-4.0. More preferably, it is part by mass. If it is more than the said lower limit, it is excellent in heat resistance. On the other hand, if it is below the said upper limit, the resist composition of this invention can be made into a highly sensitive resist composition.

  Specific examples of the surfactant and the plasticizer include those described in JP2013-029832A.

<Combination ratio of each component in resist composition>
(B) It is preferable to mix | blend the total content of a coloring material in the ratio of 3-65 mass% with respect to solid content whole quantity of a resist composition, More preferably, it is 4-55 mass%. If it is more than the said lower limit, the colored layer at the time of apply | coating a resist composition to predetermined | prescribed film thickness (usually 1.0-5.0 micrometers) has sufficient color density. Moreover, if it is below the said upper limit, while being excellent in storage stability, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained.
Further, the total content of (A) the dispersant and other dispersants is not particularly limited as long as (B) the color material can be uniformly dispersed. 3-60 mass parts can be used with respect to 100 mass parts of solid content of a composition. Furthermore, it is preferable to mix | blend in the ratio of 5-50 mass parts with respect to 100 mass parts of solid content of a resist composition, and it is preferable to mix | blend especially in the ratio of 10-40 mass parts. If it is more than the said lower limit, it is excellent in the dispersibility and dispersion stability of a coloring material, and is excellent in storage stability. Moreover, if it is below the said upper limit, developability will become favorable. The mass of the (A) dispersant is selected from the group consisting of a polymer having the structural unit represented by the general formula (I), an acidic group that forms a salt with the polymer, and an ester group thereof. It is the total mass with the halogenated hydrocarbon which has 1 or more types of functional groups which may have a hetero atom.
The total amount of (D) alkali-soluble resin, (E) polyfunctional monomer, and (F) photoinitiator is 10 to 92 mass%, preferably 15 to 87 mass%, based on the total solid content of the resist composition. It is preferable to mix | blend in the ratio of%. If it is more than the said lower limit, the colored layer which has sufficient hardness and adhesiveness with a board | substrate can be obtained. Moreover, if it is below the said upper limit, it is excellent in developability and generation | occurrence | production of the fine wrinkles by heat shrink is also suppressed.
Moreover, what is necessary is just to set suitably content of (C) solvent in the range which can form a colored layer accurately. Usually, it is preferably in the range of 55 to 95% by mass, more preferably in the range of 65 to 88% by mass, based on the total amount of the resist composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

<Method for producing resist composition>
The method for producing the resist composition of the present invention is not particularly limited. For example, the color material dispersion of the present invention includes (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator. It can be obtained by adding other components as necessary and mixing them using a known mixing means.

[Color filter]
The color filter according to the present invention is a color filter including at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers cures the resist composition according to the present invention. And having a colored layer formed.

  Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
At least one of the colored layers used in the color filter of the present invention is a colored layer formed by curing the resist composition according to the present invention.
The colored layer is usually formed in an opening of a light shielding part on a transparent substrate, which will be described later, and is usually composed of three or more colored patterns.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the resist composition, but is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed by the following method, for example.
First, the above-described resist composition of the present invention is applied on a transparent substrate described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a call coating method, or a spin coating method, and wet coating is performed. A film is formed.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. A photosensitive coating film is used. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the resist composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the resist composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y film (y is an arbitrary number) and three layers of Cr film may be laminated.
When the light shielding part is a material in which a black color material is dispersed or dissolved in a binder resin, the light shielding part can be formed by any method that can pattern the light shielding part, and is not particularly limited. For example, a photolithography method, a printing method, an ink jet method, or the like using a resist composition for a light shielding part can be given.

  The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black color material is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, a transparent rigid material having no flexibility such as quartz glass, alkali-free glass, or synthetic quartz plate, or a flexible or flexible resin such as a transparent resin film, an optical resin plate, or flexible glass. A transparent flexible material is mentioned.
Although the thickness of the said transparent substrate is not specifically limited, According to the use of the color filter of this invention, the thing of about 100 micrometers-1 mm can be used, for example.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter according to the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. In addition, the liquid crystal layer can be formed by overlapping the color filter and the counter substrate under reduced pressure and bonding them with a sealant. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

[Organic light emitting display]
An organic light emitting display device according to the present invention includes the above-described color filter according to the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

Synthesis Example 1 (Production of Copolymer A)
In a 500 mL round bottom four-necked separable flask equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer and digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and initiator dimethylketenemethyltrimethylsilylacetal 5.81 Part by mass was added through an addition funnel, and nitrogen substitution was sufficiently performed. 0.5 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 70.1 parts by mass of the first monomer methyl methacrylate (MMA) was added to the addition funnel. Used and added dropwise over 60 minutes. The temperature was kept below 40 ° C. by cooling the reaction flask with an ice bath. After 1 hour, 29.9 parts by mass of dimethylaminoethyl methacrylate (DMAEMA) as the second monomer was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution is reprecipitated in hexane, purified by filtration and vacuum drying, and is a basic block copolymer having a structural unit represented by the general formula (I). 107 mg KOH / g of copolymer A was obtained. The copolymer A thus obtained was confirmed by GPC (gel permeation chromatography). The weight average molecular weight Mw: 7320, the number average molecular weight Mn: 6150, and the molecular weight distribution Mw / Mn was 1.19. Met.

Synthesis Example 2 (Synthesis of copolymer B)
(1) Synthesis of Macromonomer A A reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA), and nitrogen was added. While stirring under an air stream, the temperature was raised to 90 ° C.
MMA 50.0 parts by mass, methacrylate-n-butyl (BMA) 30.0 parts by mass, benzyl methacrylate (BzMA) 20.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass A mixed solution of 1.0 part by mass of α, α′-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, followed by further reaction for 3 hours.
Next, the nitrogen stream was stopped, and the reaction solution was cooled to 80 ° C., and 8.74 parts by mass of 2-methacryloyloxyethyl isocyanate (Karenz MOI (manufactured by Showa Denko KK)), dibutyltin dilaurate was reduced to 0.8. 125 g, 0.125 parts by mass of p-methoxyphenol and 10 parts by mass of PGMEA were added and stirred for 3 hours to obtain a macromonomer A solution.

  When the obtained macromonomer A was confirmed by GPC, the weight average molecular weight (Mw) was 4010, the number average molecular weight (Mn) was 1910, and molecular weight distribution (Mw / Mn) was 2.10.

(2) Synthesis of copolymer B using macromonomer A A reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 80.0 parts by mass of PGMEA, and a nitrogen stream The mixture was heated to 85 ° C. with stirring.
146.04 parts by mass of macromonomer A solution obtained in (1) above (effective solid content 48 parts by mass), 29.9 parts by mass of DMAEMA, 1.24 parts by mass of n-dodecyl mercaptan, 20.0 parts by mass of PGMEA, AIBN0. After 5 parts by mass of the mixed solution mixed solution was added dropwise over 1.5 hours and heated and stirred for 3 hours, a mixed solution of AIBN 0.10 parts by mass and PGMEA 10.0 parts by mass was added dropwise over 10 minutes. For 1 hour to obtain a graft copolymer solution. The obtained graft copolymer solution was reprecipitated in hexane, purified by filtration and vacuum drying, and a graft copolymer having an amine value of 107 mgKOH / g having a structural unit represented by the general formula (I). A certain copolymer B was obtained. When the copolymer B thus obtained was confirmed by GPC, the weight average molecular weight (Mw) was 11480, the number average molecular weight (Mn) was 4650, and the molecular weight distribution (Mw / Mn) was 2.47. there were.

Synthesis Example 3 (Synthesis of alkali-soluble resin A)
The polymerization tank was charged with 300 parts by mass of PGMEA and heated to 100 ° C. in a nitrogen atmosphere, and then 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and perbutyl. 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining 100 ° C., and after 2 hours from the completion of dropping of the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.
Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added and the temperature was raised to 110 ° C., then 0.8 parts by mass of triethylamine was added, and the mixture was heated at 110 ° C. for 15 hours. By addition reaction, an alkali-soluble resin A (weight average molecular weight (Mw) 8500, acid value 75 mgKOH / g, solid content 40% by mass) was obtained.
In addition, the said weight average molecular weight measured the weight average molecular weight by Showex GPC system-21H (Shodex GPC System-21H) by using polystyrene as a standard substance and THF as an eluent. The acid value was measured based on JIS K 0070.

Production Example 1 (Preparation of salt copolymer A solution)
One type selected from the group consisting of an acidic group and its ester group as a modifier, in which 5.0 parts by mass of copolymer A obtained in Synthesis Example 1 is dissolved in 20.84 parts by mass of PGMEA in a 100 mL round bottom flask. 0.21 parts by mass (DMAEMA unit of copolymer A) of α-bromophenylacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a halogenated hydrocarbon having the above functional group and optionally having a hetero atom 0.1 mol equivalents) was added, and the mixture was stirred at a reaction temperature of 30 ° C. for 7 hours to obtain a salt-type copolymer A solution having a solid content of 20% by mass.

Production Examples 2 to 3 (Preparation of salt copolymer B to C solution)
In Production Example 1, the salt type copolymers B to C each having a solid content of 20% by mass were prepared in the same manner as in Production Example 1 except that the type of modifier and the modification amount were changed as shown in Table 1-1. A solution was obtained.
In addition, the amount of modifiers in Table 1-1 and Table 1-2 represents the molar equivalent of the copolymer A or the copolymer B to the DMAEMA unit.

Production Example 4 (Preparation of salt copolymer D solution)
In a 100 mL round bottom flask, 5.0 parts by mass of the copolymer A obtained in Synthesis Example 1 is dissolved in 22.12 parts by mass of PGMEA, and the modifier is selected from the group consisting of an acidic group and its ester group. 0.21 part by mass (DMAEMA of Copolymer A) of α-bromophenylacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a halogenated hydrocarbon which has a functional group of more than one species and may have a hetero atom 0.1 mol equivalent to the unit) and 0.33 parts by mass of benzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.2 mol equivalent to the DMAEMA unit of copolymer A) were added, and the reaction temperature was 30. By stirring at a temperature of 7 ° C. for 7 hours, a salt type copolymer D solution having a solid content of 20% by mass was obtained.

Production Examples 5 to 8 (Preparation of salt copolymer E to H solution)
In Production Example 1, the salt type copolymers E to H each having a solid content of 20% by mass were prepared in the same manner as in Production Example 1 except that the type of modifier and the amount of modification were changed as shown in Table 1-1. A solution was obtained.

Production Example 9 (Preparation of salt copolymer I solution)
In Production Example 4, a salt-type copolymer I solution having a solid content of 20% by mass was obtained in the same manner as in Production Example 4 except that the type and amount of the modifying agent were changed as shown in Table 1-1. .

Production Example 10 (Preparation of salt copolymer J solution)
In a 100 mL round bottom flask, 5.0 parts by mass of the copolymer B obtained in Synthesis Example 2 was dissolved in 23.28 parts by mass of PGMEA, and α-bromophenylacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a modifier. Is added in an amount of 0.82 parts by mass (0.4 molar equivalent based on the DMAEMA unit of copolymer B) and stirred at a reaction temperature of 30 ° C. for 15 hours to give a salt-type copolymer J solution having a solid content of 20% by mass. Got.

Comparative Production Examples 1 to 4 (Preparation of Comparative Salt Type Copolymer KN Solution)
In Production Example 1, except that the type of modifier and the amount of modification were changed as shown in Table 1-2, in the same manner as in Production Example 1, each of the comparative salt-type copolymers K to 20% by solid content N solution was obtained.

Comparative Production Example 5 (Preparation of Comparative Salt Type Copolymer O Solution)
In Production Example 1, the type and amount of the modifying agent were changed as shown in Table 1-2, except that the reaction temperature was changed to 80 ° C. and the reaction time was changed to 5 hours. A comparative salt type copolymer O solution having a content of 20% by mass was obtained.

Comparative Production Examples 6 to 7 (Preparation of Comparative Salt Type Copolymer P to Q Solutions)
In Production Example 1, a comparative salt-type copolymer P to Q solution having a solid content of 20% by mass was prepared in the same manner as in Production Example 1 except that the type and amount of the modifying agent were changed as shown in Table 1-2. Got.

Comparative Production Example 8 (Preparation of Comparative Salt Type Copolymer R Solution)
In Production Example 4, a comparative salt copolymer R solution having a solid content of 20% by mass was obtained in the same manner as in Production Example 4 except that the type and amount of the modifier were changed as shown in Table 1-2. It was.

Example 1
(1) Production of Colorant Dispersion B-1 16.25 parts by mass of the salt-type copolymer A solution of Production Example 1 as a dispersant and C.I. I. Pigment Blue 15: 6 (PB15: 6) 13.0 parts by mass, alkali-soluble resin A obtained in Synthesis Example 3 16.25 parts by mass, PGMEA 54.5 parts by mass, 2.0 mm zirconia beads 100 parts by mass The portion was put into a mayonnaise bin and shaken for 1 hour with a paint shaker (manufactured by Asada Tekko Co., Ltd.) as a pre-crush, then the zirconia beads having a particle size of 2.0 mm were taken out, and 200 masses of zirconia beads having a particle size of 0.1 mm In the same manner, as this crushing, dispersion was performed for 6 hours with a paint shaker to obtain a colorant dispersion B-1.

(2) Production of resist composition B-1 6.37 parts by mass of the colorant dispersion B-1 obtained in (1) above and 1.82 parts by mass of the alkali-soluble resin A obtained in Synthesis Example 3 1.09 parts by mass of polymerizable polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.) 0.26 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (photoinitiator : 0.06 parts by mass of trade name Irgacure 369, manufactured by BASF Japan), 0.07 parts by mass of fluorosurfactant (trade name MegaFac R-08MH, manufactured by DIC Corporation), and 10.33 parts by mass of PGMEA Part addition, Resist composition B-1 was obtained.

Examples 2-8
(1) Production of Color Material Dispersions B-2 to B-8 In Example 1 (1), instead of the salt copolymer A solution, the salt copolymers B of Production Examples 2 to 8, respectively. Color material dispersions B-2 to B-8 were obtained in the same manner as in Example 1 (1) except that the H solution was used.
(2) Production of resist compositions B-2 to B-8 In (2) of Example 1, the color material dispersions B-2 to B-8 were used instead of the color material dispersion B-1, respectively. Except for the above, resist compositions B-2 to B-8 were obtained in the same manner as (2) of Example 1.

Example 9
(1) Production of Color Material Dispersion B-9 In Example 1 (1), except that the salt-type copolymer A solution of Production Example 10 was used instead of the salt-type copolymer A solution. In the same manner as in Example 1 (1), a colorant dispersion B-9 was obtained.
(2) Production of Resist Composition B-9 In (2) of Example 1, Example 1 (2) except that Color Material Dispersion B-9 was used instead of Color Material Dispersion B-1. Resist composition B-9 was obtained in the same manner as 2).

Example 10
(1) Production of Colorant Dispersion B-10 Copolymer A obtained in Synthesis Example 1 was dissolved in PGMEA to obtain a copolymer A solution having a solid content of 20% by mass. Next, 13.96 parts by mass of the copolymer A solution, 0.46 parts by mass of α-bromophenylacetic acid as an acid and halogen-containing compound as a modifier (0.4% by mass with respect to the DMAEMA unit of copolymer A). Molar equivalent), 13.0 parts by mass of PB15: 6 as a pigment, 16.25 parts by mass of alkali-soluble resin A synthesized in Synthesis Example 3, 56.33 parts by mass of PGMEA, and 100 parts by mass of 2.0 mm zirconia beads. Put into mayonnaise bin, shake for 1 hour with paint shaker (manufactured by Asada Tekko Co., Ltd.) as preliminary crushing, then take out zirconia beads with a particle size of 2.0 mm, and add 200 parts by mass of zirconia beads with a particle size of 0.1 mm. In addition, similarly, as this crushing, dispersion was performed for 6 hours with a paint shaker to obtain a colorant dispersion B-10.

(2) Production of Resist Composition B-10 In (2) of Example 1, Example 1 (2) except that Color Material Dispersion B-10 was used instead of Color Material Dispersion B-1. Resist composition B-10 was obtained in the same manner as 2).

Comparative Example 1
(1) Production of Comparative Colorant Dispersion B-11 In Example 1 (1), instead of the salt copolymer A solution, the PGMEA solution of the copolymer A obtained in Synthesis Example 1 (solid content) Comparative colorant dispersion B-11 was obtained in the same manner as (1) of Example 1 except that 20% by mass) was used.
(2) Production of Comparative Resist Composition B-11 Example 1 except that Comparative Color Material Dispersion B-11 was used instead of Color Material Dispersion B-1 in Example 2 (2). Comparative resist composition B-11 was obtained in the same manner as in (2).

Comparative Examples 2-8
(1) Production of Comparative Colorant Dispersions B-12 to B-18 In Example 1 (1), instead of the salt copolymer A solution, the comparative salt copolymers of Comparative Production Examples 1 to 7 Comparative colorant dispersions B-12 to B-18 were obtained in the same manner as in Example 1 (1) except that K and comparative salt copolymer M to R solutions were used.
(2) Production of Comparative Resist Compositions B-12 to B-18 In (2) of Example 1, the above comparative color material dispersions B-12 to B-18 were used instead of the color material dispersion B-1. Comparative resist compositions B-12 to B-18 were obtained in the same manner as (2) of Example 1 except that was used.

Comparative Example 9
(1) Production of Comparative Colorant Dispersion B-19 In Comparative Example 1 (1), Comparative Example 1 (1) was used except that Copolymer B of Synthesis Example 2 was used instead of Copolymer A. ), A comparative color material dispersion B-19 was obtained.
(2) Production of Comparative Resist Composition B-19 In Example 1 (2), Example 1 was used except that the comparative color material dispersion B-19 was used instead of the color material dispersion B-1. Comparative resist composition B-19 was obtained in the same manner as in (2).

Example 11
(1) Production of Color Material Dispersion R-1 In (1) of Example 1, instead of PB15: 6, C.I. I. Pigment Red 177 (PR177) was used in the same manner as in (1) of Example 1 except that the salt type copolymer I solution of Production Example 9 was used instead of the salt type copolymer A solution. Material dispersion R-1 was obtained.
(2) Production of Resist Composition R-1 9.19 parts by mass of the colorant dispersion R-1 obtained in (1) of Example 11 and 1.1 of the alkali-soluble resin A obtained in Synthesis Example 3. 27 parts by mass, 0.76 parts by mass of polymerizable polyfunctional monomer (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 0.18 parts by mass of 1-one (photoinitiator: trade name Irgacure 907, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 ( Photoinitiator: 0.04 parts by mass of trade name Irgacure 369, manufactured by BASF Japan), 0.07 parts by mass of a fluorosurfactant (trade names MegaFac R-08MH, manufactured by DIC Corporation), and 8 PGMEA .49 parts by mass In addition, a resist composition R-1 was obtained.

Example 12
(1) Production of Color Material Dispersion R-2 In Example 11 (1), except that the salt-type copolymer B solution of Production Example 2 was used instead of the salt-type copolymer I solution. In the same manner as in No. 11 (1), a colorant dispersion R-2 was obtained.
(2) Production of Resist Composition R-2 In Example 11 (2), except that the color material dispersion R-2 was used in place of the color material dispersion R-1, ( Resist composition R-2 was obtained in the same manner as 2).

Comparative Example 10
(1) Production of Comparative Colorant Dispersion R-3 In Example 11 (1), instead of the salt copolymer I solution, the PGMEA solution (solid content) of the copolymer A obtained in Synthesis Example 1 Comparative colorant dispersion R-3 was obtained in the same manner as (1) of Example 11 except that 20% by mass) was used.
(2) Production of Comparative Resist Composition R-3 In Example 11 (2), Example 11 was used except that the comparative color material dispersion R-3 was used instead of the color material dispersion R-1. Comparative resist composition R-3 was obtained in the same manner as (2).

Comparative Examples 11-13
(1) Production of Comparative Colorant Dispersions R-4 to R-6 In Example 11 (1), instead of the salt copolymer I solution, each was changed to the salt copolymer of Table 3 In the same manner as in Example 11 (1), comparative colorant dispersions R-4 to R-6 were obtained.
(2) Production of Comparative Resist Compositions R-4 to R-6 In (2) of Example 11, the comparative color material dispersions R-4 to R-6 were used in place of the color material dispersion R-1. Comparative resist compositions R-4 to R-6 were obtained in the same manner as (2) of Example 11 except that they were used.

Example 13
(1) Production of colorant dispersion G-1 In Example 11 (1), instead of PR177, C.I. I. Pigment Green 58 (PG58) in 11.7 parts by mass; I. Example 11 (1) except that 1.3 parts by mass of CI Pigment Yellow 150 (PY150) was used and the salt type copolymer I solution of Production Example 9 was used instead of the salt type copolymer A solution. Similarly, a color material dispersion G-1 was obtained.
(2) Production of resist composition G-1 In Example 11 (2), except that the above-mentioned color material dispersion G-1 was used instead of the color material dispersion R-1, ( In the same manner as in 2), a resist composition G-1 was obtained.

Example 14
(1) Production of Colorant Dispersion G-2 In Example 13 (1), except that the salt-type copolymer B solution of Production Example 2 was used instead of the salt-type copolymer I solution. In the same manner as in (1) of No. 13, a colorant dispersion G-2 was obtained.
(2) Production of Resist Composition G-2 In Example 13 (2), Example 13 (2) except that the color material dispersion G-2 was used instead of the color material dispersion G-1. In the same manner as in 2), a resist composition G-2 was obtained.

Comparative Example 14
(1) Production of Comparative Color Material Dispersion G-3 In Example 13 (1), instead of the salt copolymer I solution, the PGMEA solution (solid content) of the copolymer A obtained in Synthesis Example 1 Comparative colorant dispersion G-3 was obtained in the same manner as in Example 13 (1) except that 20% by mass) was used.
(2) Production of Comparative Resist Composition G-3 Example 13 except that the comparative color material dispersion G-3 was used in place of the color material dispersion G-1 in (2) of Example 13. Comparative resist composition G-3 was obtained in the same manner as in (2).

Comparative Example 15
(1) Production of Comparative Colorant Dispersion G-4 In Example 13 (1), except that the salt-type copolymer I solution was replaced with a salt-type copolymer L solution, the same as in Example 13 Comparative colorant dispersion G-4 was obtained in the same manner as (1).
(2) Production of Comparative Resist Composition G-4 Example 13 except that the comparative color material dispersion G-4 was used in place of the color material dispersion G-1 in (2) of Example 13. Comparative resist composition G-4 was obtained in the same manner as in (2).

Evaluation method <Viscosity stability evaluation of colorant dispersion>
For the colorant dispersions obtained in Examples and Comparative Examples, the viscosity immediately after preparation and after storage for 30 days at 25 ° C. are measured, the rate of change in viscosity is calculated from the viscosity before and after storage, and the viscosity stability is evaluated. did. The viscosity was measured at 25.0 ± 0.5 ° C. using a rotational vibration viscometer. The results are shown in Tables 2-4.
(Viscosity stability evaluation criteria)
A: Change rate of viscosity before and after storage is less than 15% B: Change rate of viscosity before and after storage is 15% or more and less than 25% C: Change rate of viscosity before and after storage is 25% or more Color if evaluation result is A The material dispersion is excellent in dispersion stability and can be used practically without any problem.

<Contrast evaluation>
The resist compositions obtained in the examples and comparative examples were each applied on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm using a spin coater. Then, the 2.5-micrometer-thick colored layer was formed by drying for 3 minutes at 80 degreeC using a hotplate. The colored layer was irradiated with ultraviolet rays of 60 mJ / cm ² using a high pressure mercury lamp and a super high pressure mercury lamp.
Next, the colored substrate was post-baked for 30 minutes in a clean oven at 230 ° C., and the parallel luminance and orthogonal luminance of the obtained colored substrate were measured.
The luminance was measured using a contrast measuring device CT-1 manufactured by Aisaka Electric Co., Ltd. (light source: F10 lamp between cold cathodes, luminance meter: LS-100 manufactured by Konica Minolta).

Using the measured luminance value obtained by the above luminance measurement, the contrast was derived from the following equations.
Contrast = parallel luminance (cd / m ² ) / orthogonal luminance (cd / m ² )
The evaluation of the contrast of each resist composition was performed by determining a reference resist composition and calculating the contrast with the contrast as a reference at a 100 fraction (%) with respect to each contrast. Specifically, the contrast of the resist compositions B-1 to B-19 is the same as that of the resist composition B-11 of Comparative Example 1 (resist composition using the copolymer A not subjected to salt modification as a dispersant). The contrast of the resist compositions R-1 to R-6 was determined based on the resist composition R-3 of Comparative Example 10 (resist composition using the copolymer A without salt modification as a dispersant). The contrast of resist compositions G-1 to G-4 is based on the contrast of G-3 (resist composition using copolymer A which is not salt-modified) as a dispersant. did. The results are shown in Tables 2-4.

<Development residue evaluation>
The resist compositions obtained in the examples and comparative examples were each applied on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm using a spin coater. Then, the 2.5-micrometer-thick colored layer was formed by drying for 3 minutes at 80 degreeC using a hotplate. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer is sufficiently wiped with a lens cleaner (trade name Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.) containing ethanol, and the degree of coloring of the lens cleaner Was visually observed. The results are shown in Tables 2-4.
(Development residue evaluation criteria)
A: The lens cleaner was not colored at all.
B: No residue was observed on the glass substrate, but the lens cleaner was slightly colored.
C: Residue was confirmed on the glass substrate, and clear coloring was observed in the lens cleaner.
If the development residue evaluation standard is A or B, it is evaluated that the generation of the development residue is sufficiently suppressed, and it can be used practically without any problem.

<Development time evaluation>
The resist compositions obtained in the examples and comparative examples were each applied on a glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) having a thickness of 0.7 mm and a size of 100 mm × 100 mm using a spin coater. Then, the 2.5-micrometer-thick colored layer was formed by drying for 3 minutes at 80 degreeC using a hotplate. This colored layer was irradiated with ultraviolet rays of 60 mJ / cm 2 through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer is formed is shower-developed using an aqueous 0.05% by weight potassium hydroxide solution as an alkaline developer, and the unexposed portion of the colored layer is completely dissolved. The time until the glass surface of the formed part appeared was measured as the development time. The results are shown in Tables 2-4.

[Summary of results]
From the results of Tables 2 to 4, it is a polymer having a structural unit represented by the general formula (I) as a dispersant, and at least one of the amino groups of the structural unit represented by the general formula (I). The colorant dispersions of Examples 1 to 14 using a polymer formed by salt formation of a part and a compound having at least one functional group selected from the group consisting of an acidic group and an ester group thereof and a halogen atom It was revealed that the dispersion stability of the coloring material is excellent. In addition, the resist compositions of Examples 1 to 14 prepared using the color material dispersions of Examples 1 to 14 are excellent in contrast because of excellent dispersibility of the color material, excellent in developability, and further have a development residue. Did not occur.
In Comparative Examples 2 to 5 using benzyl bromide or benzyl chloride as the modifying agent, although the dispersion stability of the color material was good, development residue was observed. Since Comparative Example 4 has the same alkali development speed as that of Example 1, it has been clarified that the generation of development residue cannot be suppressed if the alkali development speed is high. Further, in Comparative Examples 6 and 7 using a compound having an acidic group such as acetic acid or monobenzyl phthalate as the modifier, the development rate was generated although the alkali development speed was high. Further, in Comparative Example 8 in which benzyl bromide and monobenzyl phthalate were used in combination as modifiers, development residues were observed. From this, it became clear that even when a compound having a halogen atom and a compound having an acidic group or an acid ester are used in combination as the modifier, the development residue cannot be suppressed.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (9)

A colorant dispersion containing (A) a dispersant, (B) a colorant, and (C) a solvent, wherein (A) the dispersant is a structural unit represented by the following general formula (I) A polymer having at least a part of an amino group of the structural unit represented by the general formula (I), and at least one functional group selected from the group consisting of an acidic group and an ester group thereof A colorant dispersion which is a polymer formed by salt formation with a halogenated hydrocarbon which may have a hetero atom.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, and R ² and R ³ each independently include a hydrogen atom or a hetero atom. And R ² and R ³ may be bonded to each other to form a ring structure, and R ² and R ³ may be the same or different from each other.   The halogenated hydrocarbon which has 1 or more types of functional groups selected from the group which consists of the said acidic group and its ester group, and may have a hetero atom has an aromatic ring. Color material dispersion.   The said acidic group in the halogenated hydrocarbon which has 1 or more types of functional groups selected from the group which consists of the said acidic group and its ester group, and may have a hetero atom is a carboxyl group. The colorant dispersion described in 1. A method for producing a colorant dispersion containing (A) a dispersant, (B) a colorant, and (C) a solvent,
A halogen having a hetero atom having a polymer having a structural unit represented by the following general formula (I), one or more functional groups selected from the group consisting of an acidic group and an ester group thereof One or more functional groups selected from the group consisting of at least a part of the amino group of the structural unit represented by the general formula (I) and the acidic group and ester group thereof And (A) preparing a dispersant by salt formation with a halogenated hydrocarbon which may have a hetero atom,
(C) In the presence of the dispersing agent (A) in a solvent, (B) a step of dispersing the coloring material, and a method for producing a coloring material dispersion.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, and R ² and R ³ each independently contain a hydrogen atom or a hetero atom. Represents a good hydrocarbon group, and R ² and R ³ may be bonded to each other to form a ring structure, and R ² and R ³ may be the same or different from each other. A method for producing a colorant dispersion containing (A) a dispersant, (B) a colorant, and (C) a solvent,
(C) a solvent, a polymer having a structural unit represented by the following general formula (I), and one or more functional groups selected from the group consisting of an acidic group and an ester group thereof, and a heteroatom Mixing the halogenated hydrocarbon which may have and (B) the coloring material, at least a part of the amino group of the structural unit represented by the general formula (I), the acidic group and its ester group A colorant having a step of dispersing (B) a colorant while forming a salt with a halogenated hydrocarbon which has one or more functional groups selected from the group consisting of and may have a hetero atom A method for producing a dispersion.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, A is a direct bond or a divalent linking group, and R ² and R ³ each independently contain a hydrogen atom or a hetero atom. Represents a good hydrocarbon group, and R ² and R ³ may be bonded to each other to form a ring structure, and R ² and R ³ may be the same or different from each other.   A resist composition comprising the colorant dispersion according to any one of claims 1 to 3, (D) an alkali-soluble resin, (E) a polyfunctional monomer, and (F) a photoinitiator.   A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is formed by curing the resist composition according to claim 6. A color filter comprising:   8. A liquid crystal display device comprising: the color filter according to claim 7; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   An organic light emitting display device comprising the color filter according to claim 7 and an organic light emitter.

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