JP2010209160A - Pigment dispersion composition - Google Patents

Abstract

[PROBLEMS] To achieve high display performance by suppressing or preventing surface roughness even after processing such as development, post-baking, and UV cleaning in the molding process of a color filter, exhibiting high contrast when used as a color filter. And a pigment dispersion composition exhibiting high dispersion stability.
A pigment dispersion composition comprising organic pigment fine particles and a polymer compound having a pigment adsorbing group, wherein the organic pigment fine particles comprise an organic pigment solution in which an organic pigment is dissolved in a good solvent; A pigment dispersion composition which is a build-up pigment fine particle which is compatible with a solvent and deposited by mixing with a poor solvent which is a poor solvent for the organic pigment.
[Selection figure] None

Description

  The present invention relates to a pigment dispersion composition containing fine particles of build-up pigment, a colored photosensitive resin composition using the same, an inkjet ink for a color filter, a photosensitive resin transfer material, a color filter using the same, and a liquid crystal display Relates to the device.

  In recent years, the quality of image-related precision equipment such as a color image sensor and a color liquid crystal display device has been rapidly improved and its application has been rapidly expanded. Reflecting this, improvement of display performance including contrast has been strongly demanded for color filters. From this point of view, regarding color materials for color filters, organic pigments have been used in place of dyes, and recently, there are demands for pigment fine particles that are stable at the nanometer size and monodispersed. Yes. Furthermore, a novel method for producing a color filter using an ink jet technique has been studied. Thus, a drastic improvement in design freedom and a drastic reduction in cost are expected, and there is a demand for a dispersion composition of pigment fine particles suitable for this and exhibiting sufficient performance.

Here, regarding the method for producing organic pigment particles, breakdown methods such as a bead mill method and a salt milling method are common. In the milling method, it takes a lot of time and energy to sufficiently refine the organic pigment and disperse it in the composition. Also, the types of pigment that can be used are limited. As the pigment is refined, the dispersion composition may exhibit a high viscosity, and in some cases, the dispersion composition may gel during storage.
On the other hand, recently, a method for producing a pigment dispersion composition having high dispersion safety has been developed by a build-up method. This method is suitable for obtaining fine pigment particles, and specifically, a method of mixing a pigment solution and a poor solvent to precipitate nanoparticles and adding a predetermined polymer compound is disclosed ( (See Patent Documents 1 and 2). An attempt has been made to produce a color filter using this dispersion composition and to increase the contrast thereof.

JP 2007-262378 A JP 2008-083089 A

According to the dispersion compositions described in Patent Documents 1 and 2 described above, there is an effect of increasing the contrast when a color filter is used. On the other hand, the color filter is usually subjected to processing such as development, post-baking, and UV cleaning when it is molded, which may cause roughness (surface irregularities) on the surface of the colored film. When the surface of the colored film is rough, there are problems that the chromaticity and dimensional accuracy of the color filter to be manufactured are lowered and the contrast is remarkably deteriorated. The inventors pay attention to this point, and particularly in the color filter produced using a dispersion composition containing pigment fine particles prepared by a build-up method (hereinafter sometimes simply referred to as “build-up pigment fine particles”). The purpose was to solve specific problems.
That is, the present invention is intended to provide a pigment dispersion composition suitable for the production of a color filter containing build-up pigment fine particles, exhibiting high contrast when used as a color filter, and developing in the color filter molding process. Pigment dispersion composition that achieves good display performance by suppressing or preventing surface roughness even after processing such as post-baking and UV cleaning, and exhibits high dispersion stability, and colored photosensitive resin composition using the same It is an object of the present invention to provide a product, an inkjet ink for a color filter, a photosensitive resin transfer material, a color filter using the same, and a liquid crystal display device.

一般式（Ｉ）及び（II）中、Ｒ^１〜Ｒ^６は、各々独立に、水素原子又は１価の有機基を表す。Ｘ^１及びＸ^２は、各々独立に、−ＣＯ−、−Ｃ（＝Ｏ）Ｏ−、−ＣＯＮＨ−、−ＯＣ（＝Ｏ）−、又はフェニレン基を表す。Ｌ^１及びＬ^２は、各々独立に、単結合又は２価の有機連結基を表す。Ａ^１及びＡ^２は、各々独立に、１価の有機基を表す。ｍ及びｎは、各々独立に、２〜８の整数を表す。ｐ及びｑは、各々独立に、１〜１００の整数を表す。］
［Ｃ：主鎖にアクリル酸を５〜３０質量％共重合した高分子化合物。］
［Ｄ：下記一般式（３１）及び一般式（３２）からなる群より選ばれる少なくとも一種の繰り返し単位を有する高分子化合物。］
一般式（３１）
−Ｑ^１−Ｑ^２−Ｚ−
ここで Ｑ^１は −（Ｃ＝Ｏ）− または −ＳＯ_２− を、
Ｑ^２は −ＮＨ− または −ＣＨＲ^１− を、
Ｚは −（Ｃ＝Ｏ）−Ｒ^２− または −ＳＯ_２−Ｒ^２− を示す。
また Ｒ^１は 水素原子、ハロゲン原子、シアノ基、またはアルキル基を、
Ｒ^２は アルキレン基、シクロアルキレン基、またはアリーレン基を示す。
また、Ｒ^１とＲ^２とは互いに連結基を介して連結してもよい。
一般式（３２）
−Ｒｆ−ＯＨ
ここで、Ｒｆは 少なくとも１つのフッ素原子が置換したアルキレン基を示す。
（２）前記Ｄ群の高分子化合物において、前記一般式（３１）及び（３２）からなる群より選ばれる少なくとも一種の繰り返し単位が５〜１００質量％含まれることを特徴とする（１）記載の顔料分散組成物。
（３）前記高分子化合物が質量平均分子量１０００〜１０００００であることを特徴とする（１）または（２）に記載の顔料分散組成物。
（４）前記高分子化合物が、酸基を５０ｍｇＫＯＨ／ｇ以上２００ｍｇＫＯＨ／ｇ以下の範囲で有することを特徴とする（１）〜（３）のいずれか１項に記載の顔料分散組成物。
（５）（１）〜（４）のいずれか１項に記載された顔料分散組成物と、バインダーと、モノマーもしくはオリゴマーと、光重合開始剤もしくは光重合開始剤系とを含むことを特徴とする着色感光性樹脂組成物。
（６）（１）〜（４）のいずれか１項に記載された顔料分散組成物と、バインダーと、モノマーもしくはオリゴマーとを含有するカラーフィルタ用インクジェットインク。
（７）仮支持体上に、少なくとも、（５）に記載の着色感光性樹脂組成物を含む感光性樹脂層を設けたことを特徴とする感光性樹脂転写材料。
（８）（５）に記載の着色感光性樹脂組成物、（６）に記載のカラーフィルタ用インクジェットインク、及び／又は（７）に記載の感光性樹脂転写材料を用いて作製したことを特徴とするカラーフィルタ。
（９）（８）に記載のカラーフィルタを備えたことを特徴とする液晶表示装置。
（１０）有機顔料微粒子と高分子化合物を含有する顔料分散組成物の製造方法であって、
前記高分子化合物が下記Ａ〜Ｄの群から選ばれる少なくとも一種であり、
前記有機顔料微粒子が、良溶媒に有機顔料を溶解した有機顔料溶液と、前記良溶媒と相溶性でありかつ前記有機顔料に対しては貧溶媒となる貧溶媒とを混合して析出させた有機顔料微粒子であり、
かつ
（１）前記有機顔料微粒子を凝集体として析出後に濃縮ペースト化
（２）少なくとも前記高分子化合物と前記ペーストを用い、再分散
する工程を経ることを特徴とする顔料分散組成物の製造方法。
［Ａ：側鎖に複素環を有する高分子化合物。］
［Ｂ：下記一般式（Ｉ）及び（ＩＩ）の群から選ばれる少なくとも一種の繰り返し単位を含む高分子化合物。

一般式（Ｉ）及び（II）中、Ｒ^１〜Ｒ^６は、各々独立に、水素原子又は１価の有機基を表す。Ｘ^１及びＸ^２は、各々独立に、−ＣＯ−、−Ｃ（＝Ｏ）Ｏ−、−ＣＯＮＨ−、−ＯＣ（＝Ｏ）−、又はフェニレン基を表す。Ｌ^１及びＬ^２は、各々独立に、単結合又は２価の有機連結基を表す。Ａ^１及びＡ^２は、各々独立に、１価の有機基を表す。ｍ及びｎは、各々独立に、２〜８の整数を表す。ｐ及びｑは、各々独立に、１〜１００の整数を表す。］
［Ｃ：主鎖にアクリル酸を５〜３０質量％共重合した高分子化合物。］
［Ｄ：下記一般式（３１）及び一般式（３２）からなる群より選ばれる少なくとも一種の繰り返し単位を有する高分子化合物。］
一般式（３１）
−Ｑ^１−Ｑ^２−Ｚ−
ここで Ｑ^１は −（Ｃ＝Ｏ）− または −ＳＯ_２− を、
Ｑ^２は −ＮＨ− または −ＣＨＲ^１− を、
Ｚは −（Ｃ＝Ｏ）−Ｒ^２− または −ＳＯ_２−Ｒ^２− を示す。
また Ｒ^１は 水素原子、ハロゲン原子、シアノ基、またはアルキル基を、
Ｒ^２は アルキレン基、シクロアルキレン基、またはアリーレン基を示す。
また、Ｒ^１とＲ^２とは互いに連結基を介して連結してもよい。
一般式（３２）
−Ｒｆ−ＯＨ
ここで、Ｒｆは 少なくとも１つのフッ素原子が置換したアルキレン基を示す。 The above problems have been achieved by the following means.
(1) A pigment dispersion composition containing organic pigment fine particles and a polymer compound,
The organic pigment fine particles are formed by mixing an organic pigment solution obtained by dissolving an organic pigment in a good solvent, and a poor solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. Pigment fine particles,
The pigment dispersion composition, wherein the polymer compound is at least one selected from the following groups A to D.
[A: a polymer compound having a heterocyclic ring in the side chain. ]
[B: a polymer compound containing at least one repeating unit selected from the group of the following general formulas (I) and (II).

In general formulas (I) and (II), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. L ¹ and L ² each independently represents a single bond or a divalent organic linking group. A ¹ and A ² each independently represents a monovalent organic group. m and n each independently represents an integer of 2 to 8. p and q each independently represent an integer of 1 to 100. ]
[C: a polymer compound obtained by copolymerizing 5 to 30% by mass of acrylic acid in the main chain. ]
[D: A polymer compound having at least one repeating unit selected from the group consisting of the following general formula (31) and general formula (32). ]
General formula (31)
-Q ¹ -Q ² -Z-
Where Q ¹ represents — (C═O) — or —SO ₂ —,
Q ² represents —NH— or —CHR ¹ —,
Z represents — (C═O) —R ² — or —SO ₂ —R ² —.
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group,
R ² represents an alkylene group, a cycloalkylene group, or an arylene group.
R ¹ and R ² may be linked to each other via a linking group.
Formula (32)
-Rf-OH
Here, Rf represents an alkylene group substituted with at least one fluorine atom.
(2) The high molecular compound of the group D contains 5 to 100% by mass of at least one repeating unit selected from the group consisting of the general formulas (31) and (32) (1) Pigment dispersion composition.
(3) The pigment dispersion composition according to (1) or (2), wherein the polymer compound has a mass average molecular weight of 1,000 to 100,000.
(4) The pigment dispersion composition according to any one of (1) to (3), wherein the polymer compound has an acid group in a range of 50 mgKOH / g to 200 mgKOH / g.
(5) The pigment dispersion composition described in any one of (1) to (4), a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system, A colored photosensitive resin composition.
(6) An ink-jet ink for a color filter comprising the pigment dispersion composition described in any one of (1) to (4), a binder, and a monomer or oligomer.
(7) A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (5) is provided on a temporary support.
(8) A colored photosensitive resin composition according to (5), an inkjet ink for a color filter according to (6), and / or a photosensitive resin transfer material according to (7). Color filter.
(9) A liquid crystal display device comprising the color filter according to (8).
(10) A method for producing a pigment dispersion composition containing organic pigment fine particles and a polymer compound,
The polymer compound is at least one selected from the following groups A to D;
The organic pigment fine particles are deposited by mixing an organic pigment solution in which an organic pigment is dissolved in a good solvent, and a poor solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. Pigment fine particles,
And (1) a method of producing a pigment dispersion composition, wherein the organic pigment fine particles are precipitated as aggregates and then concentrated to paste (2), and at least the polymer compound and the paste are used for redispersion.
[A: a polymer compound having a heterocyclic ring in the side chain. ]
[B: a polymer compound containing at least one repeating unit selected from the group of the following general formulas (I) and (II).

In general formulas (I) and (II), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. L ¹ and L ² each independently represents a single bond or a divalent organic linking group. A ¹ and A ² each independently represents a monovalent organic group. m and n each independently represents an integer of 2 to 8. p and q each independently represent an integer of 1 to 100. ]
[C: a polymer compound obtained by copolymerizing 5 to 30% by mass of acrylic acid in the main chain ]
[D: a polymer compound having at least one repeating unit selected from the group consisting of the following general formula (31) and general formula (32). ]
General formula (31)
-Q ¹ -Q ² -Z-
Where Q ¹ represents — (C═O) — or —SO ₂ —,
Q ² represents —NH— or —CHR ¹ —,
Z represents — (C═O) —R ² — or —SO ₂ —R ² —.
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group,
R ² represents an alkylene group, a cycloalkylene group, or an arylene group.
R ¹ and R ² may be linked to each other via a linking group.
Formula (32)
-Rf-OH
Here, Rf represents an alkylene group substituted with at least one fluorine atom.

The pigment dispersion composition of the present invention is suitable for production of a color filter containing build-up pigment fine particles, exhibits a high contrast when made into a color filter, and also develops, post-bake, UV cleaning, etc. in the molding process of the color filter. Pigment dispersion composition that achieves good display performance by suppressing or preventing surface roughness even after treatment, and exhibits high dispersion stability, colored photosensitive resin composition using the same, inkjet ink for color filter, In addition, a photosensitive resin transfer material can be provided.
In addition, by using a pigment dispersion composition having the above-mentioned good characteristics, a colored photosensitive resin composition prepared using the same, an inkjet ink for a color filter, and a photosensitive resin transfer material, there is no surface roughness and precision optics. It is possible to provide a high-performance color filter that can be suitably used for devices and the like, and to provide a liquid crystal display device that can display a vivid image using the color filter.

Hereinafter, the present invention will be described in detail.
The kind of the organic pigment used in the pigment dispersion composition of the present invention is not limited in terms of hue. For example, perylene compound pigment, perinone compound pigment, quinacridone compound pigment, quinacridone quinone compound pigment, anthraquinone compound pigment, Anthrone compound pigment, benzimidazolone compound pigment, disazo condensation compound pigment, disazo compound pigment, azo compound pigment, indanthrone compound pigment, phthalocyanine compound pigment, triarylcarbonium compound pigment, dioxazine compound pigment, aminoanthraquinone compound pigment, diketo Examples include pyrrolopyrrole compound pigments, thioindigo compound pigments, isoindoline compound pigments, isoindolinone compound pigments, pyranthrone compound pigments, isoviolanthrone compound pigments, and mixtures thereof. .

  Among these, a perylene compound pigment, a quinacridone compound pigment, an anthraquinone compound pigment, a diketopyrrolopyrrole compound pigment, an aminoanthraquinone compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment is preferable, and a diketopyrrolopyrrole compound More preferred are pigments, aminoanthraquinone compound pigments, phthalocyanine compound pigments, dioxazine compound pigments, or azo compound pigments.

  In the present invention, two or more kinds of organic pigments or solid solutions of organic pigments may be used in combination, or may be used in combination with organic dyes.

  In the present invention, it is preferable to use the following specific polymer compounds A to D, and the mass average molecular weight thereof is 1000 to 500,000 (although more preferable ranges in each polymer compound will be described individually if necessary). Is more preferable, 2000 to 300000 is more preferable, and 3000 to 200000 is particularly preferable. In the present invention, the molecular weight means a mass average molecular weight unless otherwise specified, and the mass average molecular weight (Mw) is a polystyrene equivalent mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The polymer compound having a heterocyclic ring in the side chain in the present embodiment may further contain copolymer units derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

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

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

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

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

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

[Polymer Compound B]
The pigment dispersion composition of the present invention comprises a polymer compound containing at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II) (hereinafter referred to as “specific polymer”). It may be referred to as “.”).

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

R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, a substituted or unsubstituted alkyl group is preferable. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.
When the alkyl group has a substituent, examples of the substituent include a hydroxy group, an alkoxy group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, A 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group are exemplified.
R ¹ , R ² , R ⁴ , and R ⁵ are preferably hydrogen atoms, and R ³ and R ⁶ are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency on the pigment surface.

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

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

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

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

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

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

  m and n each independently represents an integer of 2 to 8. In view of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.

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

  As the specific polymer in this embodiment, those containing a repeating unit represented by the general formula (I) are preferable from the viewpoint of dispersion stability.

  Moreover, as a repeating unit represented by general formula (I), it is more preferable that it is a repeating unit represented by the following general formula (I) -2.

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

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

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

  Below, the preferable specific example [monomer (A-1)-(A-23)] of the monomer represented by general formula (i), (ii), or (i) -2 is given to the following. However, the present invention is not limited to these.

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

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

  The specific polymer in the present embodiment includes a monomer having a functional group that can be adsorbed to the pigment and the above-described general formulas (i), (ii), and (i) -2 for the purpose of enhancing adsorption to the pigment. It is preferable that it is a high molecular compound which copolymerized the monomer represented. Specific examples of the monomer having a functional group that can be adsorbed to the pigment include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Among these, monomers having an organic dye structure or a heterocyclic structure are preferable from the viewpoint of the adsorptive power to the pigment.

  The monomer having an organic dye structure or a heterocyclic structure is preferably one selected from the group consisting of a monomer represented by the following general formula (11), a maleimide, and a maleimide derivative. Among these, a monomer represented by the following general formula (11) is particularly preferable.

In the general formula (11), R ¹ represents a hydrogen atom or an alkyl group. R ² represents a single bond or a divalent linking group. Y represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. Z represents a group having a nitrogen-containing heterocyclic group.

As the alkyl group represented by R ¹ in the general formula (11), an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. preferable.
When the alkyl group represented by R ¹ has a substituent, the substituent is preferably, for example, an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, or a cyclohexyloxy group. As this alkoxy group, a C1-C5 thing is preferable and a C1-C3 thing is preferable.

Specific examples of preferable alkyl group represented by R ¹ in the general formula (11) include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n- Examples include a hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.
Among them, R ¹ is most preferably a hydrogen atom or a methyl group.

The divalent linking group represented by R ² in the general formula (11) is preferably an alkylene group or a divalent group containing an alkylene group. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, still more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. Particularly preferred.
When this alkylene group has a substituent, examples of the substituent include a hydroxy group.
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

As the divalent group containing an alkylene group represented by R ² in the general formula (11), two or more of the above alkylene groups linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom) It may be.
The divalent group containing an alkylene group represented by R ^2, the end towards which binds to Z in the alkylene group, -O -, - S -, - C (= O) O -, - CONH-, -C (= O) S-, -NHCONH-, -NHC (= O) O-, -NHC (= O) S-, -OC (= O)-, -OCONH-, and -NHCO- A hetero atom selected from or a partial structure containing a hetero atom may be bonded.

Specific examples of the nitrogen-containing heterocyclic structure constituting the nitrogen-containing heterocyclic group represented by Z in the general formula (11) include, for example, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, and triazole ring. , Tetrazole ring, indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure The thing which has is mentioned.
These nitrogen-containing heterocyclic structures may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, and an alkoxycarbonyl group. Is mentioned.

The nitrogen-containing heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Particularly preferred is a group having
Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea A structure and a cyclic imide structure are preferable, and a structure represented by the following general formula (12), (13) or (14) is particularly preferable.

In the general formula (12), X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), -O-, -S-, -NR ^A- , and It is one selected from the group consisting of —C (═O) —. Here, R ^A represents a hydrogen atom or an alkyl group. When R ^A represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as X in the general formula (12), a single bond, a methylene group, —O—, or —C (═O) — is preferable, and —C (═O) — is particularly preferable.

In the general formula (14), Y and Z are each independently, -N =, - NH -, - N (R B) -, - S-, or an -O-. R ^B represents an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among the above, as Y and Z in the general formula (14), —N═, —NH—, and —N (R ^B ) — are particularly preferable. Preferred examples of the combination of Y and Z include a combination (imidazolyl group) in which one of Y and Z is —N═ and the other is —NH—.

  In general formula (12), (13), or (14), ring A, ring B, ring C, and ring D each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring. Are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

Specifically, examples of the ring A and ring B in the general formula (12) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Examples of the ring C in the general formula (13) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
Examples of the ring C in the general formula (14) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.

  Among the structures represented by the general formula (12), (13) or (14), a benzene ring or a naphthalene ring is more preferable from the viewpoint of dispersibility and stability over time of the dispersion, and the general formula (12) or In (14), a benzene ring is more preferred, and in general formula (13), a naphthalene ring is more preferred.

  In addition, the maleimide derivative in the present invention means a maleimide in which the N position is substituted with a substituent such as an alkyl group or an aryl group.

  Hereinafter, preferred specific examples (monomers M-1 to M-33) of the monomer represented by the general formula (11), maleimide, and maleimide derivatives are listed below, but the present invention is limited thereto. It is not a thing.

  The specific polymer in this embodiment includes only one type of repeating unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (11), maleimide, and maleimide derivatives. It may contain, and may contain 2 or more types.

In the specific polymer in the present embodiment, the content of the repeating unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (11), maleimide, and maleimide derivatives is: When the total repeating unit contained in the polymer is 100% by mass, the content is preferably 5% by mass or more, and more preferably 10% by mass to 50% by mass.
That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is represented by the general formula (11). The content of polymerized units derived from one monomer selected from the group consisting of monomers, maleimides, and maleimide derivatives is preferably 5% by mass or more. Moreover, from the viewpoint of developability when producing a color filter with a colored photosensitive composition containing a pigment dispersion composition, the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives The content of polymerized units derived from one more selected monomer is preferably 50% by mass or less.

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

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

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

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

  As a monomer having a basic nitrogen atom, (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1 -(N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N -Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) Piperidinoethyl acrylate, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ) Ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1 , 1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like Examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene and the like.

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers). Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having an acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like. As the vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyldiallylane Such as salt, and the like.

  The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

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

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

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

A preferred embodiment of the specific copolymer in the present embodiment includes at least a monomer represented by the general formula (i), (ii), or (i) -2, and a monomer having an organic dye structure or a heterocyclic structure. More preferably, at least a monomer represented by the above general formula (i) -2, a monomer represented by the above general formula (11), and an acid group. And a monomer having the same.
According to this embodiment, it is possible to provide a pigment dispersion composition having excellent pigment adsorption and excellent developability.

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

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

  In the pigment dispersion composition of the present embodiment, the content of the specific polymer is preferably a mass ratio of pigment: specific polymer = 1: 0.1 to 1: 2, more preferably 1: 0.2 to 1: 1, and more preferably 1: 0.4-1: 0.7.

  Moreover, in the range which does not impair the effect of this embodiment, you may use another high molecular compound simultaneously with the above-mentioned specific copolymer as needed. As other polymer compounds, natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used. The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins. Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.

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

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

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

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

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

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

Examples of the acid group represented by the general formula (32) include —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, —CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

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

一般式（Ｇ−Ｉ）〜（Ｇ−ＩＩＩ）で、Ｒ^３は水素原子、またはメチル基を表す。Ｓ^１は上記一般式（１−ａ）〜（１−ｆ）で表される連結基を表す。Ｒは、置換基を有していても良いアルキル基、シクロアルキル基またはアリール基を表す。Ｒｆは、少なくとも１つのフッ素原子が置換したアルキレン基を示す。Ｗ^２は、単結合または、

（Ｚ^１、Ｚ^２は水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、シアノ基、ヒドロキシル基を表し、Ｚ^３は水素原子、炭素原子数１〜１８のアルキル基、炭素原子数６〜２０のアリール基を表す。）等の原子団から選ばれた単独の連結基もしくは任意の組合せで構成された連結基を表す。 Specifically, the polymer compound may introduce the general formulas (31) and (32) by polymerizing monomers represented by the following general formulas (GI) to (G-III). It is possible and preferable.

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

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

（Ｗ^１はアルキレン、アルコキシ、エステルから選ばれた単独の連結基もしくは任意の組合せで構成された連結基を表す。Ｓ^１は上記一般式（１−ａ）〜（１−ｆ）で表される連結基を表す。Ｒ¹は、置換基を有していても良いアルキル基、シクロアルキル基または
アリール基を表す。Ｒ^２は水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、アルコキシ基、シアノ基を表す。Ｒ^３は水素原子、またはメチル基を表す。Ｒｆは、少なくとも１つのフッ素原子が置換したアルキレン基を示す。） The general formulas (GI) to (G-III) are preferably represented by the following general formulas (G-IV) to (G-VII).

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

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

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

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

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

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

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

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

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

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid. And mono (1-methyl-2-acryloyloxyethyl ester). The acid group can be introduced separately from the acid group described above.

  Examples of the monomer having a basic nitrogen atom include vinyl pyridine, vinyl imidazole, vinyl triazole and the like as monomers having a heterocyclic ring, and (meth) acrylic acid ester as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, ( (Meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, (meth) acrylic acid N, N-di-n-butylaminoethyl, (meth) acrylic acid N, N- Di-i-butylaminoethyl, morpholinoethyl (meth) acrylate, piperidy (meth) acrylate Ethyl, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate, and N, N-methylphenylaminoethyl (meth) acrylate, and the like ( As meta) acrylamides, N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′-diethylaminoethyl) acrylamide N- (N ′, N′-diethylaminoethyl) methacrylamide, N- (N ′, N′-dimethylaminopropyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- ( N ', N'-diethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylate Luamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide , Morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc., and styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, etc. .

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

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

  The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

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

  The monomer constituting the block (c) that is not adsorbed on the pigment is not particularly limited, and examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, and fumaric acid diesters. Itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like can be mentioned. These monomers may be used independently and may use 2 or more types together.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, (meth) a 2-ethoxyethyl laurate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, vinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, (meth ) 1-propenyl acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth ) Diethylene glycol monoethyl ether acrylate, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene Glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryl Trifluoroethyl acid, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyloxyethyl and (meth) acrylic acid γ-butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

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

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

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

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
Examples of (meth) acrylonitrile include methacrylonitrile and acrylonitrile.

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

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

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

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

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

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

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

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

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

  Moreover, as a polymerization initiator which can introduce | transduce a functional group into a polymer terminal, for example, 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 4,4'- Azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2, 2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide ] Or this Like derivatives of.

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

  The organic pigment fine particles in the present invention are prepared by mixing a solution in which an organic pigment is dissolved in a good solvent and a solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment, so that the organic pigment becomes fine particles Precipitated build-up pigment fine particles. Here, the combination of the good solvent and the poor solvent preferably has a sufficient difference in solubility of the organic pigment, and it is preferable to select a preferable one according to the organic pigment, but it is a combination that enables the process in the present invention. Any choice is possible.

  The good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent. As for the solubility of the organic pigment in a good solvent, the solubility of the organic pigment is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility of the organic pigment in the good solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali.

  Examples of the good solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, and a fat. Group compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compounds Solvents, ester compound solvents, amide compound solvents, or mixtures thereof are preferred, aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, aqueous solvents, sulfoxide compound solvents or amide compounds. More preferably medium, sulfoxide compound solvent or the amide compound solvent is particularly preferred.

  Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

The concentration of the solution in which the organic pigment is dissolved in the good solvent is preferably in the range of the saturated concentration of the organic pigment to the good solvent or about 1/100 of this in the dissolving conditions.
There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  There are some common examples of those listed as specific examples of good solvents and those listed as poor solvents, but the same solvents are not combined as good solvents and poor solvents. It is sufficient that the solubility in is sufficiently higher than the solubility in a poor solvent. For example, the solubility difference is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the difference in solubility between the good solvent and the poor solvent, it is practical that the difference is 50% by mass or less in consideration of a commonly used organic pigment.

  When the organic pigment is uniformly dissolved in a good solvent, a dissolution accelerator such as acid or alkali may be added and dissolved. Generally, in the case of a pigment having an alkaline dissociable group in the molecule, the addition of an alkali is performed. When there is no alkaline dissociable group and there are many nitrogen atoms or the like in the molecule that are prone to add protons, an acid is added. Is preferred. For example, quinacridone, diketopyrrolopyrrole and disazo condensation compound pigments are alkaline and dissolved. Phthalocyanine compound pigments are dissolved in an acidic manner, but some of them are dissolved in an alkaline manner, and the mechanism of dissolving in an alkaline manner is not clear.

  Examples of the alkali include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide, or organic bases such as trialkylamine, diazabicycloundecene (DBU), and metal alkoxide. Of these, trialkylamines and metal alkoxides are preferable, and metal alkoxides are more preferable. The amount of alkali added is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, and 1.0 Particularly preferred is ˜20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the organic pigment.

  Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, or organic acids such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Among them, inorganic acids are preferable. More preferably, it is sulfuric acid. The amount of acid to be added is not particularly limited, but it is often used in excess compared to the base. Regardless of the inorganic acid and organic acid, the organic pigment is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and particularly preferably 30 to 200 molar equivalents. .

  When mixing alkali or acid with an organic solvent and using it as a good solvent for organic pigments, a solvent having high solubility in some alkali or acid such as water or lower alcohol in order to completely dissolve the alkali or acid Can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the organic pigment solution. Although there is no restriction | limiting in particular in the lower limit of this quantity, Usually, it is 0.01 mass% or more. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

  The viscosity of the organic pigment solution is preferably 0.5 to 80.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  Although a poor solvent is not specifically limited, It is preferable that the solubility of an organic pigment is 0.02 mass% or less, and it is more preferable that it is 0.01 mass% or less. Although there is no particular lower limit to the solubility of the organic pigment in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.

  Examples of the poor solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, Examples thereof include nitrile compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, and mixed solvents thereof, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof are preferable. An aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.

Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran, and the like. Examples of the aromatic compound solvent include benzene and toluene. Examples of the aliphatic compound solvent include hexane. Examples of the nitrile compound solvent include acetonitrile. Examples of the halogen compound solvent include dichloromethane and trichloroethylene. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

  The first good solvent and the second good solvent may be the same or different, but it is preferable to use the same type or the same type in combination. The first poor solvent and the second poor solvent may be the same or different, but it is preferable to use the same type or the same type in combination.

  There are no particular limitations on the conditions of the poor solvent when the pigment fine particles are precipitated and produced, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C.

  When mixing the organic pigment solution and the poor solvent, either of them may be added and mixed, but it is preferable to jet the organic pigment solution into the poor solvent and mix, and the poor solvent is stirred at that time. It is preferable that the The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

By adjusting the Reynolds number when mixing the organic pigment solution and the poor solvent, the particle diameter of the pigment fine particles to be formed can be controlled. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Equation (1), Re represents the Reynolds number, ρ represents the density [kg / m ³ ] of the organic pigment solution, and U represents the relative velocity [m / s] when the organic pigment solution and the poor solvent meet. L represents the equivalent diameter [m] of the flow path or supply port where the organic pigment solution and the poor solvent meet, and μ represents the viscosity coefficient [Pa · s] of the organic pigment solution.

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

  The relative speed U when the organic pigment solution and the poor solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the organic pigment solution is injected and mixed in a stationary poor solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the organic pigment solution is a value determined by the type of material selected, but is, for example, 0.8 to 2.0 kg / m ³ in the range of materials preferably used in the production method of the present invention. That is practical. Also, the viscosity coefficient μ of the organic pigment solution is a value determined by the material used, the environmental temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the organic pigment solution described above.

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

The mixing ratio of the organic pigment solution and the poor solvent is preferably 1/50 to 2/3 by volume, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8.
When pigment fine particles are precipitated, the particle concentration in the liquid is not particularly limited, but the pigment fine particles are preferably in the range of 10 to 40000 mg, more preferably in the range of 20 to 30000 mg, particularly preferably 1000 ml of the solvent. Is in the range of 50-25000 mg.
Moreover, the preparation scale at the time of producing | generating a pigment microparticles | fine-particles is although it does not specifically limit, It is preferable that the mixing amount of a poor solvent is a 10-2000L preparation scale, and it is more preferable that it is a 50-1000L preparation scale.

  Regarding the particle size of pigment fine particles, there is a method of expressing the average size of the population by quantifying it by a measurement method, but the mode diameter indicating the maximum value of the distribution and the median value of the integral distribution curve are often used. Median diameter, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle diameter is the number average. The diameter. The average particle size of the pigment fine particles (primary particles) is a nanometer size, the average particle size is preferably 1 nm to 0.5 μm, more preferably 1 to 200 nm, and further preferably 2 to 100 nm. Preferably, it is 5-80 nm, and it is especially preferable. The particles formed by the production method of the present invention may be crystalline particles, amorphous particles, or a mixture thereof.

Further, in the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1. 5 is particularly preferred.
Examples of the method for measuring the particle size of the pigment fine particles include a microscope method, a mass method, a light scattering method, a light blocking method, an electric resistance method, an acoustic method, and a dynamic light scattering method. Particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus based on the dynamic light scattering method include Nikkiso's Nanotrac UPA-EX150, Otsuka Electronics' dynamic light scattering photometer DLS-7000 series (both are trade names), and the like.

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

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

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

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

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

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

  When a nitrogen-containing polymer compound is used as the polymer compound, as the particle size adjusting agent, a particle size adjusting agent composed of a polymer compound having an acidic group and a particle size adjusting agent composed of a compound having a basic nitrogen atom are used in combination. Preferably not. Moreover, when using the high molecular compound which has an acidic group as the said high molecular compound, it is preferable not to use together the particle size adjusting agent which consists of a nitrogen-containing high molecular compound as a particle size adjusting agent.

  The content of the particle size adjusting agent is preferably in the range of 0.1 to 1000% by mass, more preferably 1 to 500% by mass with respect to the pigment in order to further improve the particle size control of the pigment fine particles. More preferably, it is the range of 5-200 mass%. In addition, the particle size adjusting agents may be used alone or in combination.

  In the present invention, after pigment fine particles are precipitated, it is preferable to reduce or remove the solvent content of the dispersion containing the precipitated particles (hereinafter, this operation may be simply referred to as concentration). Thereby, it can be set as the nanoparticle concentrate and pigment fine particle powder suitable for a color filter coating liquid and an inkjet ink.

In the present invention, a normal apparatus can be used alone or in combination for the concentration of the solvent. For example, as dryers using hot air, shelf dryers, band dryers, stirring dryers, fluidized bed dryers, spray dryers, air dryers, etc., dryers using heat conduction are drum dryers, multiple dryers, etc. A tube dryer, a cylindrical dryer or the like is preferably used. Depending on the solvent composition, a freeze dryer or an infrared dryer can be used.
Among these means, a spray dryer (for example, COC-12 [trade name] manufactured by Okawara Kako Co., Ltd.), fluidized bed, is suitable for obtaining a pigment fine powder dried directly from the dispersion. A dryer (for example, MSD-100 [trade name] manufactured by Nara Machinery Co., Ltd.) is particularly preferably used. In addition, a plurality of drying means may be used in combination to obtain a pigment fine particle powder with a small residual solvent amount. For example, the pigment dispersion composition pre-concentrated with a cylindrical dryer is completely dried with a drum dryer. A process such as obtaining pigment particulate powder can be used.
The drying conditions are not particularly limited as long as the solvent can be evaporated and materials such as pigments and dispersants are not denatured. Of course, when other dispersants are denatured at a lower temperature, it is necessary to lower the temperature. However, depending on the type of solvent used, the drying speed may be reduced within the allowable temperature range. In this case, for the purpose of increasing the drying speed, depending on the type of dryer, means such as decompression, stirring and mixing, multiple stages, etc. Can be combined.

The amount to reduce or remove the solvent content is not particularly limited, but in an embodiment in which the solvent content is reduced, it is preferable to remove 50% by mass or more of the total solvent content, and more preferably 75% by mass or more. In an embodiment in which the solvent content is removed to obtain pigment fine particle powder, it is preferable to remove 80% by mass or more, and more preferably 90% by mass or more, of the total solvent content.
When the solvent content is reduced by reducing or removing the solvent content, the water content in the remaining dispersion composition is not particularly limited, but is preferably 0.01 to 3% by mass, 0.01 to More preferably, the content is 1% by mass. At this time, for example, it is preferable to remove the solvent by the above drying method or the like to obtain pigment fine particle powder. At this time, the solid content is preferably 50 to 100% by mass, and 70 to 100% by mass. It is more preferable.
The concentration step may be performed multiple times.

  The polymer compound A used as a preferred embodiment of the present invention is preferably added before the final concentration step. By doing so, the surface of the pigment fine particles is coated with the polymer compound A, and the formation of aggregates of the pigment fine particles during concentration can be effectively suppressed, or the cohesive force can be effectively weakened. A dispersion in a state close to particles can be obtained, and a color filter with high contrast can be obtained.

  The pigment fine particles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used for forming the pigment fine particles and the binder used for redispersion may be the same or different.

The pigment fine particle concentration of the pigment dispersion composition of the present invention is appropriately determined according to the purpose, but preferably the pigment fine particle content is preferably 2 to 30% by mass and 4 to 20% by mass with respect to the total amount of the dispersion composition. More preferably, it is particularly preferably 5 to 15% by mass.
In the case of dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

In the concentrated pigment fine particle liquid with a reduced solvent content, the nanoparticles may aggregate as described above. As a method of redispersing such aggregated pigment fine particles, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs (see Non-Patent Document 1). Therefore, the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
There are no particular restrictions on the dispersing machine used to disperse the pigment fine particles concentrated by applying physical energy. Is mentioned. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  The colored photosensitive resin composition includes a dispersion composition of the organic pigment fine particles, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

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

The monomer or oligomer is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
Monomers or oligomers may be used alone or in admixture of two or more. The content of the colored photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

  As the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing an inkjet ink or a colored photosensitive resin composition, but it is added at the time of producing the pigment fine particle dispersion composition or at the time of forming pigment fine particles. Is also preferable. It is also possible to add a binder to both or one of the poor solvent for adding the organic pigment solution and the organic pigment solution to form pigment fine particles. Alternatively, it is also preferable to add a binder solution when forming fine pigment particles in a separate system. The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. The binder may be used alone or may be used in the state of a composition used in combination with a normal film-forming polymer, and the addition amount relative to 100 parts by mass of pigment fine particles is generally 10 to 200 parts by mass. Yes, 25-100 mass parts is preferable.

As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds), U.S. Pat. No. 2,367,660 Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon-substituted fragrances described in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, combinations of triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones, Benzothiazole compounds and trihalomethyl-s-triazines described in Japanese Patent No. 51-48516 Compound, trihalomethyl are described in U.S. Patent No. 4239850 - triazine compounds include U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.
The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low. The radiation that can be used for exposure is particularly preferably ultraviolet rays such as g-line and i-line. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably ^{10~1000mJ / cm 2, 10~500mJ / cm} 2 is particularly preferred.

  In the colored photosensitive resin composition, in addition to the above components, an organic solvent for preparing a resin composition (fourth solvent) may be further used. Examples of the fourth solvent include, but are not limited to, esters, ethers, and ketones. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent. These solvents may be used alone or in combination of two or more. The high-boiling organic solvent can be used as the fourth solvent. For example, a solvent having a boiling point of 180 ° C. to 250 ° C. can be used if necessary. As for content of a 4th solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

  The colored photosensitive resin composition can contain a surfactant, a thermal polymerization inhibitor, a colorant (dye, pigment), an ultraviolet absorber, an adhesion aid, other additives, and the like.

In addition to the color filter, the inkjet ink of the present invention may be a normal inkjet ink for image formation or the like. In particular, the inkjet ink for a color filter is preferable. The ink jet ink is not particularly limited as an embodiment in the present invention, but for example, a method described in JP-A-2002-201387 can be preferably used.
The inkjet ink of the present invention may be any ink using the organic pigment fine particles (a), and preferably further contains a binder (b) and a monomer or oligomer (c). Here, as a binder (b) monomer or oligomer (c), what was previously demonstrated in the colored photosensitive resin composition can be used. The inkjet ink of the present invention may further contain a photopolymerization initiator or a photopolymerization initiator system (d) and other additives. The content of each component ((a) to (d), other additives) may be the same as that described above for the colored photosensitive composition. However, when the inkjet ink of the present invention is used as an ink for preparing a color filter, an embodiment that is not a photosensitive ink is preferable, and it is preferable not to use a photopolymerization initiator or a photopolymerization initiator system.

For ink-jet ink, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. For example, the surface tension is platinum by using a measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

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

  In the present invention, it is preferable that a partition wall is prepared in advance and ink is applied to a portion surrounded by the partition wall before forming a pixel using the color filter inkjet ink. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix.

  Said colored photosensitive resin composition can be apply | coated by the normal apply | coating method, and a coating film can be formed by drying it. Examples of the coating method include coating with a slit nozzle, spin coating, and the like.

  The photosensitive transfer material of the present invention has a photosensitive resin layer containing the above-described colored photosensitive resin composition, and the specific configuration is not particularly limited. For example, an integrated film is used. It is preferable that it is formed. As an example of the structure of the integral film, a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film is laminated in this order can be given.

  In the photosensitive transfer material, it is necessary that the temporary support has flexibility and does not cause significant deformation, contraction or elongation even under pressure, or under pressure and heat. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

In the photosensitive transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from ordinary ones. Of these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

The photosensitive transfer material is provided with a thermoplastic resin layer by applying a coating solution (thermoplastic resin coating solution) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the resin layer, and then the photosensitive resin layer is prepared by applying and drying with a solvent that does not dissolve the intermediate layer. Can do.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In the photosensitive transfer material, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

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

  When the color filter of the present invention is used for a television, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below ( Hereinafter, in the present invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

  The liquid crystal display device provided with the color filter of the present invention has a high contrast and excellent descriptive power such as black spots, and the VA system is particularly preferable. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. The color filter of the present invention can be used for a CCD device and exhibits excellent performance.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

<Synthesis Example 1>
(Synthesis of P-1 of Polymer Compound A)
The M-6 27.0 g, MMA 126.0 g, MAA 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd .: Three One) The mixture is stirred with a motor and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.80 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% by mass solution of polymer compound P-1 was obtained.
It was 21,000 as a result of measuring the mass mean molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content was 99 mgKOH / g from the titration using sodium hydroxide.

<Synthesis Example 2>
(Synthesis of P-2 and P-3 of polymer compound B)
Into a 500 mL three-necked flask, 160.0 g of ε-caprolactone and 18.3 g of 2-ethyl-1-hexanol were introduced, and dissolved by stirring while blowing nitrogen. Monobutyltin oxide 0.1 g was added and heated to 100 ° C. After 8 hours, it was cooled to 80 ° C. after confirming disappearance of the raw material by gas chromatography. After adding 0.1 g of 2,6-di-t-butyl-4-methylphenol, 22.2 g of 2-methacryloyloxyethyl isocyanate was added. After 5 hours, after confirming disappearance of the raw material by H NMR, the mixture was cooled to room temperature to obtain 200 g of a solid monomer (A-5). It was confirmed by H NMR, IR, and mass spectrometry that it was a monomer (A-5).
The obtained monomer (A-5) is mentioned as a preferred specific example of the monomer represented by the general formula (i), (ii), or (i) -2.

37.5 g of monomer (A-5), monomer M-115.0 g, methacrylic acid 7.5 g, dodecyl mercaptan 1.3, and 16.7 g of 1-methoxy-2-propanol were substituted with nitrogen. The mixture was introduced into the flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 75 ° C. while flowing nitrogen into the flask. To this was added 0.3 g of 2,2-azobis (2,4-dimethylvaleronitrile) (“V-65” manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. After 2 hours, 0.3 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer compound P-2 was obtained.
It was 18,000 as a result of measuring the mass mean molecular weight of the obtained high molecular compound P-2 by the gel permeation chromatography method (GPC) which used the polystyrene as a reference material. Polymer compound P-3 was prepared in the same manner except that the monomers used in the synthesis of polymer compound P-2 and the amounts thereof were replaced with the monomers and amounts shown in the following table. The following table shows the monomers used when synthesizing the polymer compounds P-2 and P-3, the amount charged, the mass average molecular weight of the synthesized polymer, and the acid value.

<Synthesis Example 3>
(Synthesis of polymer compound C P-4, P-5, P-6)
(Polymer Compound P-4)
M-11 (Exemplary compound M-11 in the description of the polymer compound B) 14.0 g, 105.0 g of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toagosei Co., Ltd.), acrylic acid 21. 0 g, 5.6 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), and heated while flowing nitrogen into the flask. The temperature is raised to 75 ° C. 1.1 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added thereto, and the mixture was stirred with heating at 75 ° C. for 2 hours. Thereafter, 1.1 g of V-601 was further added and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours to obtain a 30% solution of polymer compound P-4.
As a result of measuring the mass average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 19000.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from 1H-NMR was 20/65/15.

(Polymer Compound P-5)
Polymer compound A-16 was synthesized by the same method as A-5 used for the synthesis of polymer compound P-4.
15.0 g of M-11, 105.0 g of A-16 synthesized above, 21.0 g of acrylic acid, 3.1 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, and a stirrer (new The mixture is stirred with Toshin Kagaku Co., Ltd .: Three-One Motor, and heated to 75 ° C. while flowing nitrogen into the flask. To this was added 1.2 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.2 g of V-601 was further added, and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and heated and stirred for 2 hours, and then a 30% solution of polymer compound P-5 was obtained.
It was 23,000 as a result of measuring the mass mean molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

(Polymer Compound P-6)
28.0 g of benzyl methacrylate, 91.0 g of A-16 synthesized above, 21.0 g of acrylic acid, 4.2 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The temperature is increased to 75 ° C. by heating while stirring with nitrogen (Scientific Co., Ltd .: Three-One Motor). To this, 1.0 g of 2,2-azobis (dimethyl 2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was added, and the mixture was heated and stirred at 75 ° C. for 2 hours. Thereafter, 1.0 g of V-601 was further added, and the mixture was heated and stirred for 2 hours, then heated to 90 ° C. and stirred for 2 hours, and then a 30% solution of polymer compound P-6 was obtained.
It was 21,000 as a result of measuring the mass mean molecular weight of the obtained high molecular compound by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance.
From the titration using sodium hydroxide, the acid value per solid content was 117 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from ¹ H-NMR was 20/65/15.

<Synthesis Example 4>
(Synthesis of polymer compound C P-7 and P-8)
In a 1 L three-necked flask, 69 g of methacrylamide, 136 g of triethylamine, and 130 mL of tetrahydrofuran were mixed and ice-cooled. To this solution, 161 g of camphor-sulfonyl chloride dissolved in 200 mL of tetrahydrofuran was added dropwise over 1.5 hours and stirred for 1 hour. After completion of the reaction, the mixture was neutralized with 2 mol / L dilute hydrochloric acid and extracted twice with ethyl acetate. The oil layer was extracted with 2 mol / L sodium hydroxide aqueous solution. The aqueous layer was ice-cooled, and hydrochloric acid was added dropwise for crystallization. The precipitated white crystals were collected by filtration and washed with water to obtain 103 g of the desired compound G-1.

¹ H-NMR (400 MHz, CDCl ₃ ) was measured to identify the compound.
δ 0.91 (S, 3H), 1.08 (S, 3H), 1.47 (td, 1H), 2.03 (M, 4H), 2.00 (S, 3H), 2.36 ( M, 2H), 3.38 (D, 1H), 3.93 (D, 1H), 5.65 (D, 1H), 5.92 (D, 1H), 8.65 (bs, 1H)

21.0 g of BzMA, 91.0 g of polymethyl methacrylate having a methacryloyl group at the end (AA-6: manufactured by Toa Gosei Co., Ltd.), 21.0 g of G-1, 2.9 g of n-dodecyl mercaptan and 327 g of methoxypropylene glycol Then, the mixture is introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three One Motor), heated while flowing nitrogen into the flask, and heated to 78 ° C. To this was added 0.8 g of 2,2-azobis (dimethyl 2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 78 ° C. for 2 hours. Two hours later, 0.8 part of V-601 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer compound C P-7 was obtained. From the titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g.
Similarly, P-8 of the polymer compound C was synthesized.

[Table P] Figures in parentheses are mass%.
------------------------------------
No. Composition of constituent units Mass average molecular weight Acid value (mgKOH / g)
------------------------------------
P-1 M-6 (15) MMA (70) MAA (20) 21,000 98
P-2 A-5 (75) M-11 (10) MAA (15) 18,000 99
P-3 A-5 (75) BzMA (10) MAA (15) 18,000 97
P-4 M-11 (75) AA-6 (10) AA (15) 19,000 117
P-5 A-16 (75) M-11 (10) AA (15) 23,000 117
P-6 A-16 (65) BzMA (20) AA (15) 21,000 117
P-7 BzMA (20) AA-6 (65) G-1 (15) 20,000 98
P-8 a-1 (20) AA-6 (65) G-13 (15) 23,000 85
------------------------------------
AA: acrylic acid MAA: methacrylic acid MMA: methyl methacrylate M-11: a repeating unit represented by the above general formula (11) BzMA: benzyl methacrylate AA-6: methacryloylated polymethyl methacrylate oligomer at one end
(Mn = 6000, manufactured by Toagosei Chemical Industry Co., Ltd.)

(Example 1 and Comparative Example 1)
<Preparation of organic pigment dispersion composition>
(Comparative Example 1)
To 1000 ml of dimethyl sulfoxide, 33.3 ml of 28% methanol solution of sodium methoxide, pigment C.I. I. Pigment Red 254: trade name Irgafore Red BT-CF Ciba Specialty Chemicals Co., Ltd.) 50 g and polyvinyl pyrrolidone 100.0 g were added to prepare a pigment solution A. Separately, 1000 ml of water containing 16 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.
Here, NP-KX-500 manufactured by Nippon Seimitsu Chemical Co., Ltd. was added to 1000 ml of poor solvent water, which was temperature-controlled at 18 ° C. and stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer manufactured by Fujisawa Pharmaceutical. Organic pigment particles were formed by injecting 100 ml at a flow rate of 100 ml / min using a large-capacity non-pulsating flow pump to prepare pigment dispersion A. The particle size and monodispersity of this pigment dispersion were measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. The results are shown in Table 1 below.
The pigment fine particle dispersion prepared by the above method is centrifuged with a high speed centrifugal cooler HIMAC SCR20B manufactured by Hitachi Koki Co., Ltd. under conditions of 3500 rpm (2000 G) for 1 hour, and the supernatant is discarded and concentrated. The paste was collected. The pigment content of the paste was measured using an Agilent 8453 type spectrophotometer and found to be 12.5% by mass.
By adding 50.0 cc of ethyl lactate to 16.0 g of the pigment fine particle preparation paste, stirring at 1500 rpm for 60 minutes with a dissolver, and then filtering using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer Co., Concentrated pigment liquid C1 (nano pigment concentration 33 mass%) was obtained.
[Preparation of pigment dispersion composition]
Using the paste, a pigment dispersion composition C1 having the following composition was prepared.
19.5 g of the paste-like concentrated pigment liquid A
Pigment dispersant A 0.6g
The following high molecular compound (C-18) 3.2g
1-methoxy-2-propyl acetate 45.3g
The pigment dispersant A was synthesized according to Japanese Patent Laid-Open No. 2000-239554.
The pigment dispersion composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger Japan) for 1 hour at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.

Example 1
After adding 0.3 g of the polymer compound P-1 shown in Table 1 (see the synthesis example) to 16 g of pigment fine particle preparation paste prepared by using the above pigment solution A without using polyvinylpyrrolidone, 50.0 cc of ethyl lactate was added. Except for the above, a pigment dispersion composition 1 was obtained in the same manner as in Comparative Example 1. The above pigment solution A was prepared without using polyvinyl pyrrolidone, and was replaced with the polymer compound C-18 in the same manner as in Comparative Example 1 except that the polymer compound shown in Table 1 (see the synthesis example) was used. Thus, pigment dispersion compositions 2 to 8 were obtained. After adding 0.3 g of the polymer compound P-1 shown in Table 1 (see the synthesis example) to 16 g of pigment fine particle preparation paste prepared by using the above pigment solution A without using polyvinylpyrrolidone, 50.0 cc of ethyl lactate was added. In addition, a pigment dispersion composition 8 was obtained in the same manner as in Comparative Example 1 except that the polymer compound P-5 shown in Table 1 was used instead of the polymer compound C-18.

[Table 1]
----------------------------------
Dispersion composition No. High molecular compound average particle size Monodispersity ---------------------------------
C1 (Comparative Example 1) C-18 33 nm 1.29
1 (Example 1-1) P-1 34 nm 1.15
2 (Example 1-2) P-2 34 nm 1.15
3 (Example 1-3) P-3 34 nm 1.15
4 (Example 1-4) P-4 34 nm 1.15
5 (Example 1-5) P-5 34 nm 1.15
6 (Example 1-6) P-6 34 nm 1.15
7 (Example 1-7) P-7 34 nm 1.15
8 (Example 1-8) P-8 34 nm 1.15
9 (Example 1-9) P-1 + P-5 34 nm 1.15
----------------------------------

(Example 2 and Comparative Example 2)
<Preparation of Color Filter 1-C1 (Preparation by Coating Using Slit Nozzle)>

[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., it is described in Table 1-1 below with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 having the composition: Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K1 was obtained.

[Table 1-1] Photosensitive resin layer K1
--------------------------------------
K pigment dispersion composition 1 (carbon black) 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization Initiator A 0.16 parts by mass Surfactant 1 0.044 parts by mass -------------------------------- -------

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials, Inc., 100-fold diluted solution) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

  For the colored photosensitive resin composition K1, first, K pigment dispersion composition 1 and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 2, Hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s -Triazine) and Surfactant 1 were weighed out, added in this order at a temperature of 25 ° C (± 2 ° C), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C (± 2 ° C).

<K pigment dispersion composition 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan)
13.1 parts by mass / dispersant (compound J) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass <DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass Propylene glycol monomethyl ether acetate 24 parts by mass <Surfactant 1>
Megafac F-780-F (Dainippon Ink and Chemicals, Inc.): composition below _{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts by weight and _{H (OCH (CH 3) CH} 2) Copolymer of ₇ OCOCH = CH ₂ 55 parts by mass and H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ 5 parts by mass (molecular weight 30,000)
30 parts by mass, 70 parts by mass of methyl ethyl ketone

[Formation of red (R) pixels]
Using the colored photosensitive resin composition R1 having the composition described in Table 1-2 below on the substrate on which the image K is formed, the heat-treated pixel R is formed in the same process as the formation of the black (K) image. did. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10

[Table 1-2] Colored photosensitive resin composition R1
--------------------------------------
Dispersion Composition C1 40 parts by mass R Pigment Dispersion Composition 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA solution 3.8 parts by mass Polymerization Initiator B 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 1 0.06 parts by mass ----------------- ---------------------

<R pigment dispersion composition 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate <Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, 73 parts by mass of propylene glycol monomethyl ether acetate <polymerization initiator B>
2-Trichloromethyl- (p-styrylstyryl) 1,3,4-oxadiazole

[Formation of green (G) pixels]
In the same process as the formation of the black (K) image, the heat-treated pixel is formed using the colored photosensitive resin composition G1 having the composition described in Table 1-3 below on the substrate on which the image K and the pixel R are formed. G was formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 1-3] Colored photosensitive resin composition G1
--------------------------------------
G pigment dispersion composition 1 (CIPG36) 28 parts by mass Y pigment dispersion composition 1 (CIPI150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 2.5 parts by mass DPHA Liquid 3.5 parts by weight Polymerization initiator B 0.12 parts by weight Polymerization initiator A 0.05 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.07 parts by weight ---------- ---------------------------

<G pigment dispersion composition 1>
"Product name: GT-2" manufactured by FUJIFILM Electronics Materials Co., Ltd.

<Y pigment dispersion composition 1>
"Product name: CF Yellow-EX3393" manufactured by Gokoku Color Co., Ltd.

[Formation of blue (B) pixels]
Using the colored photosensitive resin composition B1 having the composition described in Table 1-4 below on the substrate on which the image K, the pixel R, and the pixel G are formed, A heat-treated pixel B was formed to obtain a target color filter A1. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 1-4] Colored photosensitive resin composition B1
--------------------------------------
B pigment dispersion composition 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion composition 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 17 parts by mass DPHA solution 4 0.0 parts by mass Polymerization initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 1 0.06 parts by mass -------------------- -----------------

<B pigment dispersion composition 1>
"Product name: CF Bull-EX3357" manufactured by Gokoku Color Co., Ltd.
<B pigment dispersion composition 2>
"Product name: CF Bull-EX3383" manufactured by Gokoku Color Co., Ltd.
<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

  Color filters 1-1 to 9 were produced in the same manner except that the dispersion composition C1 was changed to the dispersion compositions 1 to 9.

[Measurement of color filter contrast]
Using the produced color filter as a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N, trade name, manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed, two polarizing plates (HLC2- 2518, trade name, manufactured by Sanritsu Co., Ltd.), measured the amount of transmitted light when the polarization axis was parallel and vertical, and the ratio was taken as contrast (Ueki, Koseki, Fukunaga, Yamanaka) , "512 color display 10.4" size TFT-LCD color filter ", 7th Color Optical Conference (1990), etc.).
The measurement results of the contrast of each color filter are shown in Table 2 below.

[Evaluation of dispersion stability over time]
The viscosity (initial viscosity) at 25 ° C. immediately after the production of the produced colored photosensitive resin composition R1 was measured. Moreover, the viscosity at 25 ° C. (viscosity with time) of the colored photosensitive resin composition stored for 2 months in an environment of 40 ° C. was measured. Table 2 shows the result of comparing the initial viscosity and the viscosity with time. At this time, the viscosity was measured using a vibration viscometer VM-100A-L [trade name].
5 Increase in viscosity was less than 1 4 Increase in viscosity was 1 or more and less than 3 3 Increase in viscosity was 3 or more and less than 5 2 Increase in viscosity was 5 or more and less than 10 1 Increase in viscosity Was over 10

[Surface roughness]
About each color filter produced as mentioned above, the degree of surface roughness of the red pixel surface was measured using an atomic force microscope (NanoScope IIIa [trade name], manufactured by Nanoworld).

[Table 2]
----------------------------
Dispersion composition Contrast Dispersion stability Surface roughness ----------------------------
C1 8000 1 21 nm
1 9900 3 8 nm
2 11000 3 9 nm
3 12000 4 5 nm
4 15000 3 6 nm
5 14000 5 7 nm
6 14000 4 6 nm
7 12000 4 5 nm
8 13000 5 7 nm
9 16000 5 6 nm
----------------------------
As is apparent from Table 2, the colored photosensitive resin composition prepared using the pigment dispersion composition of the present invention in Example 2 does not show an increase in viscosity after storage and is excellent in dispersion stability. Recognize. Moreover, it turns out that the color filter formed using this colored photosensitive resin composition can form a colored film which is excellent in contrast and has a small surface roughness.

(Example 3 and Comparative Example 3)
<Production of Color Filter 2-C1 (Production by Laminating Photosensitive Resin Transfer Material)>
[Production of photosensitive resin transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.4 μm was provided, and a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded.
Thus, a photosensitive resin transfer material K1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.36 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl
Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,
Molecular weight: 90,000, Tg: about 70 ° C.) 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight: 10,000, Tg: about 100 ° C.) 13.6 parts by mass. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.,
Product name: 2,2-bis [4- (methacryloxypolyethoxy)
Phenyl] propane) 9.1 parts by mass / surfactant 1 0.54 parts by mass

<Interlayer coating solution: Formulation P1>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts by mass / polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd.)
K-30) 14.9 parts by mass, 524 parts by mass of distilled water, 429 parts by mass of methanol

  Next, the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1 is the following colored photosensitive resin composition R2, G2 having the composition described in Tables 2-1 to 2-3 below. Photoresin transfer materials R2, G2, and B2 were prepared in the same manner as described above except that they were changed to B2 and B2. In addition, the preparation methods of colored photosensitive resin composition R2, G2, and B2 are based on the preparation method of said colored photosensitive resin composition R1, G1, and B1, respectively.

[Table 2-1] R2
--------------------------------------
Dispersion composition C1 40 parts by weight R pigment dispersion composition 2 (CIPR177) 4.5 parts by weight Propylene glycol monomethyl ether acetate 7.1 parts by weight Methyl ethyl ketone 57 parts by weight Binder 1 0.8 parts by weight DPHA solution 4.4 parts by weight Polymerization Initiator B 0.14 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Additive 1 0.52 parts by weight Surfactant 1 0.06 parts by weight ---------- ----------------------------

[Table 2-2] G2
--------------------------------------
G pigment dispersion composition 1 (CIPG36) 28 parts by mass Y pigment dispersion composition 1 (CIPI150) 13 parts by mass Propylene glycol monomethyl ether acetate 39 parts by mass Methyl ethyl ketone 16 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 3.0 parts by mass DPHA Liquid 4.3 parts by weight Polymerization initiator B 0.15 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.07 parts by weight ---------- ---------------------------

[Table 2-3] B2
--------------------------------------
B pigment dispersion composition 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion composition 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 18.5 parts by mass DPHA Liquid 4.3 parts by mass Polymerization initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 1 0.06 parts by mass ------------------ -------------------

  In addition, among the compositions described in Table 2-1, as the additive 1, a phosphate ester special activator (manufactured by Enomoto Kasei Co., Ltd., trade name: HIPLAAD ED152) was used.

[Formation of black (K) image]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm ² and a conveyance speed of 2.2 m / min.
After peeling the temporary support at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are used with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. ) Was set vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, a triethanolamine developer (containing 2.5% triethanolamine, trade name: T-PD2, Fuji Photo Film Co., Ltd., 12-fold diluted with pure water (1 part of T-PD2 The mixture was mixed at a ratio of 11 parts of water.))) At 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed.
Subsequently, sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer. A patterning image was obtained.
Subsequently, using a solution obtained by diluting a cleaning agent (trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.) 10 times with pure water, a shower and nylon hair were removed at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a rotating brush, and a black (K) image was obtained, and then post-exposure was performed on the substrate from the resin layer side with a 500 mJ / cm ² light with an ultrahigh pressure mercury lamp. It heat-processed at 15 degreeC for 15 minutes.
The substrate on which this image K was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to a substrate preheating device.

[Formation of red (R) pixels]
Using the photosensitive resin transfer material R2, a heat-treated red (R) pixel R was obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 35 ° C. for 35 seconds. The film thickness of the photosensitive resin layer RA2 and the coating amount of the pigment (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10
The substrate on which the image K and the pixel R were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of green (G) pixels]
Using the photosensitive resin transfer material G2, heat-treated green (G) pixels G were obtained in the same process as the photosensitive resin transfer material R2. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 34 ° C. for 45 seconds. The film thickness of the photosensitive resin layer G101 and the coating amount of the pigment (CIPG36 and CIPY150) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58
The substrate on which the image K, the pixel R, and the pixel G were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of blue (B) pixels]
Using the photosensitive resin transfer material B2, a heat-treated blue (B) pixel B was obtained in the same process as the photosensitive resin transfer material R2. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds. The film thickness of the photosensitive resin layer B2 and the coating amount of the pigments (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045
The substrate on which the pixel R, the pixel G, the pixel B, and the image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter.

  Color filters 2-1 to 9 were produced in the same manner except that the dispersion composition C1 was changed to the dispersion compositions 1 to 9.

  The contrast and surface roughness of the obtained color filter and the temporal stability of the colored photosensitive resin composition R2 were evaluated in the same manner as in Example 2 and Comparative Example 2. The results are shown in Table 3.

[Table 3]
--------------------------------
Dispersion composition Contrast Dispersion stability Surface roughness --------------------------------
C1 6000 1 28 nm
1 9000 3 6 nm
2 9500 4 8 nm
3 8500 4 8 nm
4 9800 4 8 nm
5 11000 3 9 nm
6 9800 5 5 nm
7 8900 4 6 nm
8 10000 5 6 nm
9 12000 5 5 nm
--------------------------------
As is apparent from Table 3, the colored photosensitive resin composition prepared using the pigment dispersion composition of the present invention of Example 3 does not show an increase in viscosity after storage and is excellent in dispersion stability. Recognize. Moreover, it turns out that the color filter formed using this colored photosensitive resin composition can form a colored film which is excellent in contrast and has a small surface roughness.

(Example 4 and Comparative Example 4)
<Production of Color Filter 3-C1 (Production by Inkjet)>
Regarding the production procedure of the photosensitive resin transfer material K1, the photosensitive resin transfer material K2 was similarly prepared except that the colored photosensitive resin composition K1 was replaced with the colored photosensitive resin composition K2 described in Table 3-1 below. Produced.

[Table 3-1] Colored photosensitive resin composition K2
--------------------------------------
K pigment dispersion composition 1 (carbon black) 30 parts by mass Propylene glycol monomethyl ether acetate 7.3 parts by mass Methyl ethyl ketone 34 parts by mass Cyclohexanone 8.6 parts by mass Binder 2 14 parts by mass DPHA solution 5.8 parts by mass Polymerization initiator A 0 .22 parts by mass Phenothiazine 0.006 parts by mass Surfactant 1 0.058 parts by mass ---------------------------- ----------

  The resin composition K2 having a light-shielding property was first weighed out K pigment dispersion composition 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.) and stirred at 150 rpm for 10 minutes, and then Table 3-1 Methyl ethyl ketone, cyclohexanone, binder 2, phenothiazine, DPHA solution, polymerization initiator A and surfactant 1 in the amounts described are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. (± 2 At 150 rpm for 30 minutes.

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

After peeling off the protective film of the photosensitive resin transfer material K2, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape is a lattice shape, and the radius of curvature of the corner convex toward the light-shielding partition wall in the portion corresponding to the boundary line between the pixel and the light-shielding partition wall is 0.6 μm.

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd. 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The resulting mixture was diluted with a mixture) at 30 ° C. for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and shower-developed at 29 ° C. for 30 seconds with a cone type nozzle pressure of 0.15 MPa to have a light shielding property Was developed to obtain a patterning separation wall (a partition wall pattern having a light shielding property).

Subsequently, using a cleaning agent (trade name “T-SD3 (manufactured by Fuji Photo Film Co., Ltd.)” diluted 10 times with pure water), a shower and nylon hair at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue was removed with a rotating brush having a light shielding property to obtain a light-shielding partition. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultra-high pressure mercury lamp from the resin layer side, and then heat treated at 240 ° C. for 50 minutes.

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

[Preparation of inkjet ink for color filter]
An inkjet ink for a color filter was prepared according to the following formulation.
[Table 3-R]
--------------------------------------
Composition component Content (parts by mass) Ink R3
--------------------------------------
Dispersion composition C1 63
R pigment dispersion composition 2 (CIPR177) 7
Polymer dispersant (Solsperse 20000 (trade name) manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------

[Table 3-G]
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Composition component Content (parts by mass) Ink G3
--------------------------------------
G pigment dispersion composition 1 (P.G.36) 35
Y pigment dispersion composition 1 (P.Y.150) 32
Polymer dispersant (Solsperse 20000 manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------

[Table 3-B]
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Composition component Content (parts by mass) Ink B3
--------------------------------------
B pigment dispersion composition 1 (P.B.15: 6 + P.V.23) 8
B pigment dispersion composition 2 (P.B.15: 6) 71
Polymer dispersant (Solsperse 20000 (trade name) manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------
Polymer 1 Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000

  Regarding the mixing of each of the components in Tables 3-R, 3-G, and 3-B, first, the pigment and the polymer dispersant are charged into a part of the solvent, mixed, and stirred using a three roll and bead mill. Thus, a pigment dispersion was obtained. On the other hand, other compounding components were added to the remainder of the solvent, and were dissolved and dispersed by stirring to obtain a monomer solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the monomer solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

[Pixel formation]
First, a color filter was prepared as follows using the ink R3, the ink G3, and the ink B3 described above.
The inkjet head used was Dimatix SE-128, and the discharge controller used was Dimatix Apollo II. An inkjet head is mounted on an automatic two-dimensional moving stage (KS211-200 manufactured by Suruga Seiki), and the stage is moved from the head by the discharge control device while moving the stage so that a predetermined amount of ink is discharged into the gap of the partition wall produced above. The discharge was synchronized.
Here, the three inks R3, G3, and B3 described above are filled in different heads, and each head is fixed on the XY stage so that each ink lands on a predetermined position. In addition, the three heads were independently controlled by the discharge control device.
For droplet ejection, the ink composition is discharged until the desired concentration is reached, heated and dried on a hot plate at 100 ° C. for 2 minutes, and then baked in a 230 ° C. oven for 30 minutes to completely cure both the partition walls and pixels. A color filter was prepared.

  Color filters 3-1 to 9 were produced in the same manner except that the dispersion composition C1 was changed to the dispersion compositions 1 to 9.

  The contrast and surface roughness of the obtained color filter and the temporal stability of the ink R3 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 4.

[Table 3]
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Dispersion composition Contrast Dispersion stability Surface roughness ----------------------------
C1 9500 1 28 nm
1 13000 4 6 nm
2 17000 4 7 nm
3 16000 4 6 nm
4 16000 3 6 nm
5 17000 4 9 nm
6 15000 3 9 nm
7 14000 3 9 nm
8 15000 3 6 nm
9 18000 5 5 nm
----------------------------
As is apparent from Table 3, the ink prepared using the pigment dispersion composition of the present invention of Example 3 shows no increase in viscosity after storage and is excellent in dispersion stability. Moreover, it turns out that the color filter formed using this colored photosensitive resin composition can form a colored film which is excellent in contrast and has a small surface roughness.

(Example 5 and Comparative Example 5)
[Production of liquid crystal display elements]
A liquid crystal display device was produced according to the following method.
(1) A patterned 1 cm ² ITO film is formed on one surface of a glass substrate, and a commercially available liquid crystal aligning agent for active matrix is applied onto the ITO film using a spinner, and then 1 at 180 ° C. The coating was dried for a time to form a coating film having a thickness of 600 mm.
(2) After forming a patterned 1 cm ² ITO film on each of the color filters 1 to 3 produced in the above-mentioned examples and comparative examples, on the ITO film, in the same manner as (1), A liquid crystal aligning agent coating was formed.
(3) After forming an ITO film (continuous film) on one surface of the glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as (1).
(4) Next, the surface of the coating film on each substrate obtained in (1) to (3) is subjected to a rubbing process using a rubbing machine provided with a roll around which a cloth made of rayon is wound, and a liquid crystal alignment film Formed. The rubbing conditions at that time were a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a push-in length of the hair foot of 0.4 mm.
(5) Of the substrates on which the liquid crystal alignment film is thus formed, each substrate that has undergone the treatment of (1) or (2) is combined with the substrate that has undergone the treatment of (3) to form a set of two pieces, For each set, an epoxy resin adhesive containing a silica gel columnar spacer with a diameter of 5.5 μm was applied to the outer edge of the two substrates by screen printing, and the rubbing direction of each liquid crystal alignment film crossed 90 degrees. As described above, the two substrates were placed opposite each other with a gap between them, and the adhesive was cured by pressing the substrates so that the outer edges of each substrate were in contact with each other.
(6) Next, for each set, nematic liquid crystal “ZLI-5081” (trade name, made of fluorobiphenyl derivative) in a cell gap defined by the inner surface of the two substrates and the hardened layer of the adhesive. After injection and filling (Merck Japan Co., Ltd.), the injection hole was sealed to prepare a liquid crystal cell. Thereafter, a polarizing plate was bonded to the outer surface of the liquid crystal cell so that the polarization direction thereof coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display element.

  The manufactured liquid crystal display device was visually evaluated for display characteristics (color unevenness, black margin). As a result, it was found that all of the liquid crystal display elements manufactured using the color filter of the present invention showed good display characteristics as compared with the liquid crystal display elements manufactured using the color filter of the comparative example. .

Claims (10)

A pigment dispersion composition containing organic pigment fine particles and a polymer compound,
The organic pigment fine particles are deposited by mixing an organic pigment solution in which an organic pigment is dissolved in a good solvent, and a poor solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. Pigment fine particles,
The pigment dispersion composition, wherein the polymer compound is at least one selected from the following groups A to D.
[A: a polymer compound having a heterocyclic ring in the side chain. ]
[B: a polymer compound containing at least one repeating unit selected from the group of the following general formulas (I) and (II).

In general formulas (I) and (II), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. L ¹ and L ² each independently represents a single bond or a divalent organic linking group. A ¹ and A ² each independently represents a monovalent organic group. m and n each independently represents an integer of 2 to 8. p and q each independently represent an integer of 1 to 100. ]
[C: a polymer compound obtained by copolymerizing 5 to 30% by mass of acrylic acid in the main chain ]
[D: a polymer compound having at least one repeating unit selected from the group consisting of the following general formula (31) and general formula (32). ]
General formula (31)
-Q ¹ -Q ² -Z-
Where Q ¹ represents — (C═O) — or —SO ₂ —,
Q ² represents —NH— or —CHR ¹ —,
Z represents — (C═O) —R ² — or —SO ₂ —R ² —.
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group,
R ² represents an alkylene group, a cycloalkylene group, or an arylene group.
R ¹ and R ² may be linked to each other via a linking group.
Formula (32)
-Rf-OH
Here, Rf represents an alkylene group substituted with at least one fluorine atom.   2. The pigment dispersion according to claim 1, wherein the polymer compound of group D contains 5 to 100 mass% of at least one repeating unit selected from the group consisting of the general formulas (31) and (32). Composition.   The pigment dispersion composition according to claim 1 or 2, wherein the polymer compound has a mass average molecular weight of 1,000 to 100,000.   The pigment dispersion composition according to any one of claims 1 to 3, wherein the polymer compound has an acid group in a range of 50 mgKOH / g to 200 mgKOH / g.   A colored photosensitive resin comprising the pigment dispersion composition according to claim 1, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Composition.   The inkjet ink for color filters containing the pigment dispersion composition as described in any one of Claims 1-4, a binder, and a monomer or an oligomer.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 5 is provided on a temporary support.   A color produced using the colored photosensitive resin composition according to claim 5, the inkjet ink for a color filter according to claim 6, and / or the photosensitive resin transfer material according to claim 7. filter.   A liquid crystal display device comprising the color filter according to claim 8. A method for producing a pigment dispersion composition containing organic pigment fine particles and a polymer compound,
The polymer compound is at least one selected from the following groups A to D;
The organic pigment fine particles are deposited by mixing an organic pigment solution in which an organic pigment is dissolved in a good solvent, and a poor solvent that is compatible with the good solvent and that is a poor solvent for the organic pigment. Pigment fine particles,
And (1) a method of producing a pigment dispersion composition, wherein the organic pigment fine particles are precipitated as aggregates and then concentrated to paste (2), and at least the polymer compound and the paste are used for redispersion.
[A: a polymer compound having a heterocyclic ring in the side chain. ]
[B: a polymer compound containing at least one repeating unit selected from the group of the following general formulas (I) and (II).

In general formulas (I) and (II), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent organic group. X ¹ and X ² each independently represent —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group. L ¹ and L ² each independently represents a single bond or a divalent organic linking group. A ¹ and A ² each independently represents a monovalent organic group. m and n each independently represents an integer of 2 to 8. p and q each independently represent an integer of 1 to 100. ]
[C: a polymer compound obtained by copolymerizing 5 to 30% by mass of acrylic acid in the main chain ]
[D: a polymer compound having at least one repeating unit selected from the group consisting of the following general formula (31) and general formula (32). ]
General formula (31)
-Q ¹ -Q ² -Z-
Where Q ¹ represents — (C═O) — or —SO ₂ —,
Q ² represents —NH— or —CHR ¹ —,
Z represents — (C═O) —R ² — or —SO ₂ —R ² —.
R ¹ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group,
R ² represents an alkylene group, a cycloalkylene group, or an arylene group.
R ¹ and R ² may be linked to each other via a linking group.
Formula (32)
-Rf-OH
Here, Rf represents an alkylene group substituted with at least one fluorine atom.