JP2019002005A - Pigment dispersion and coloring composition containing the same - Google Patents

Abstract

To provide a pigment dispersion capable of providing a coloring composition good in dispersion stability and good in storage stability even when an epoxy group-containing component is contained in a coated film formation component.SOLUTION: There is provided a pigment dispersion containing a pigment, a dispersant and a solvent, excluding quaternary ammonium salt, in which the dispersant is a block polymer having a linear structure with a first block having at least one kind selected from a constitutional unit represented by the formula (1) or the like at an end part and no basic group. Rand Rrepresent each independently H, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least one of them is not H, Rrepresents H or a monovalent hydrocarbon group having 1 to 4 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a pigment dispersion and a coloring composition containing the pigment dispersion, and in particular, a pigment dispersion used for a column spacer provided in a flat panel of a liquid crystal display device and a coloring composition containing the same. It is about.

  The liquid crystal display device has a liquid crystal cell structure in which a liquid crystal material is filled between two glass substrates provided with opposing transparent electrodes. A column spacer is inserted between the two glass substrates in order to maintain a uniform gap between the substrates and provide a good image. Conventionally, bead spacers such as bead glass have been used as such column spacers. However, the method using a bead spacer only causes beads to be dispersed randomly in the gap, which may cause a problem of light leakage, may cause a large gap distance variation, and control of mechanical properties such as elasticity. It is pointed out that there are problems such as being difficult. In addition, more precise gap control is required due to the recent demand for higher image quality for liquid crystal display devices.

  As an improvement measure, for example, a black column spacer using a black photosensitive resin composition instead of the bead spacer has been proposed (see, for example, Patent Documents 1 and 2). According to the black column spacer, it is possible to form the column spacer so that the variation in the gap distance is reduced at a desired position, and it is relatively easy to control the characteristics of the coating film forming component and the like. Therefore, when using a black column spacer, it is considered that more precise gap control is possible than with a bead spacer.

  Further, the column spacer is required to have mechanical characteristics such as compression displacement, and to be in contact with the liquid crystal substance, and therefore, is required to have resistance to the solvent contained in the liquid crystal substance, that is, solvent resistance. With respect to the solvent resistance, a certain degree of improvement is expected by using, for example, an epoxy group-containing resin.

  By the way, although it is not used as a column spacer, it contains a structural unit having an amide group in the main chain and a structural unit derived from isopropyl methacrylate in the side chain as a pigment dispersant used in a pigment dispersion for a color filter. A specific graft polymer is disclosed (Patent Document 3). According to this pigment dispersant, it is said that a cured film excellent in contrast can be formed. Also, it is not a pigment dispersion for column spacer use, but a pigment dispersion obtained by mixing an organic pigment and a specific polymer dispersant containing an amide group, and further adding a tetraalkylammonium salt for dispersion treatment. The manufacturing method of a body is disclosed (patent document 4). According to this manufacturing method, a cured film excellent in contrast can be formed.

JP 2005-191234 A Japanese Patent Laid-Open No. 2007-71994 JP 2013-125086 A JP 2013-95831 A

  According to the inventor's study, a pigment dispersion is prepared using various dispersants, and a colored composition using an epoxy group-containing component as a coating film-forming component in this manner has a problem in the development process during coating film formation. Has been found to occur. As a result of diligent investigation of this cause, a basic group such as an amine contained in a certain type of dispersant reacts with an epoxy group to change the physical properties of a coating film forming component, resulting in an extremely long development time. It has been found that there are cases where the coating cannot be performed or the coating film peels off. It has also been found that this defect is significant after storing and using the colored composition. As a result of further studies by the present inventor, it has been found that when an acid value type dispersant not containing a basic group is used, the viscosity is high, that is, the dispersion stability is poor, and it may not be used in practice. In addition, when the pigment dispersion contains a quaternary ammonium salt such as the tetraalkylammonium salt described in Patent Document 4, the coating film formed using a coloring composition containing the same deteriorates the solvent resistance. Also turned out.

  Accordingly, an object of the present invention is to provide a pigment dispersion capable of providing a coloring composition having good dispersion stability and good storage stability even when an epoxy group-containing component is contained in the coating film forming component. It is to provide a body and to provide a colored composition containing the pigment dispersion.

  As a result of the study by the present inventors, it has been found that the above-mentioned problems can be solved by using a predetermined block polymer containing an amide bond in the side chain as a dispersant, and the present invention has been completed. The gist of the present invention is as follows.

The first of the present invention is a pigment dispersion containing a pigment, a dispersant and a solvent (except for those containing a quaternary ammonium salt),
The dispersant has a linear structure having a first block having at least one selected from structural units represented by the following formulas (1), (2) and (2-2) at one end. The present invention relates to a pigment dispersion which is a block polymer having a basic group and no basic group.

(In formula (1), R ^1a and R ^1b are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. And at least one is not a hydrogen atom, a hydrogen atom directly connected to a carbon atom contained in each hydrocarbon group of R ^1a and R ^1b is —C (═O) —NR ^5a R ^5b , —O -C (= O) -NR < ^6a > R < ^6b >, -NR < ⁷ > -C (= O) -NR < ^8a > R < ^8b >, a cyclic amide group, -OH or -COOH, and an aliphatic hydrocarbon group In the case where the number of carbon atoms is 2 to 12, at least one double bond may be included in the carbon-carbon bond, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( = O) -, - C ( = O) -O -, - O-C (= O) -, - C (= O) -NR 9 - ^{-NR 10 -C (= O) -} , - NR 11 -C (= O) -O -, - O-C (= O) -NR 12 - or ^{-NR 13 -C (= O) -NR} 14 - R ^{5a to} R ¹⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ^5a and R ^5b , R ^6a and R ^6b, and R 5 ^8a and ^{R 8b} are not each of the at least one of hydrogen atom, ^{R 7} and ^{R 8a} or ^{R 8b, R 13} and ^{R 14} are each, are connected by a divalent hydrocarbon group having 1 to 4 carbon atoms ring structures In R ^1a and R ^1b , the aliphatic hydrocarbon groups having 1 to 4 carbon atoms may be connected to each other by —O— to form a ring structure.
R ² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

(In formula (2), R ³ may have a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an N—H bond, including an amide group that may have an N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group is represented.
Aliphatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 15a} R 15b, -O-C (= O) -NR 16a R 16b, -NR ¹⁷ —C (═O) —NR ^18a R ^18b , a cyclic amide group, —OH or —COOH may be substituted, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( ═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ¹⁹ —, —NR ²⁰ —C (═O) —, —NR ²¹ -C (= O) -O -, - O-C (= O) -NR 22 - or ^{-NR 23 -C (= O) -NR} 24 - may be replaced. R ^{15a to} R ²⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁷ and R ^18a or R ^18b , R ²³ and R ²⁴ each have 1 to Nitrogen atoms may be connected by a divalent hydrocarbon group of 4 to form a ring structure. In addition, when the aliphatic hydrocarbon group has 2 to 12 carbon atoms, at least one double bond may be included in the carbon-carbon bond.
Aromatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 25a} R 25b, -O-C (= O) -NR 26a R 26b, -NR ²⁷ —C (═O) —NR ^28a R ^28b , a cyclic amide group, —OH or —COOH may be substituted. R ^{25a to} R ^28b each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ²⁷ and R ^28a or R ^28b represent a divalent carbon atom having 1 to 4 carbon atoms. Nitrogen atoms may be linked by a hydrogen group to form a ring structure.
R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

(In formula (2-2), R ²⁹ and R ⁴⁵ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Represents a hydrocarbon group and at least one is not a hydrogen atom.
Aliphatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 31a} R 31b, -O-C (= O) -NR 32a R 32b, -NR ³³ —C (═O) —NR ^34a R ^34b , a cyclic amide group, —OH or —COOH may be substituted, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( ═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ³⁵ —, —NR ³⁶ —C (═O) —, —NR ^37. -C (= O) -O -, - O-C (= O) -NR 38 - or ^{-NR 39 -C (= O) -NR} 40 - may be replaced. R ^{31a to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ³³ and R ^34a or R ^34b , R ³⁹ and R ⁴⁰ , respectively, Nitrogen atoms may be connected by a divalent hydrocarbon group of 4 to form a ring structure. In addition, when the aliphatic hydrocarbon group has 2 to 12 carbon atoms, at least one double bond may be included in the carbon-carbon bond.
Aromatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 41a} R 41b, -O-C (= O) -NR 42a R 42b, -NR ⁴³ —C (═O) —NR ^44a R ^44b , a cyclic amide group, —OH or —COOH may be substituted. R ^{41a to} R ^44b each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ⁴³ and R ^44a or R ^44b are divalent carbon atoms having 1 to 4 carbon atoms. Nitrogen atoms may be linked by a hydrogen group to form a ring structure.
R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

In an embodiment of the present invention, in the structural unit represented by the formula (1), one of R ^1a and R ^{1b in} the formula (1) is a hydrogen atom,
The structural unit represented by the formula (2) is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an N— in which R ³ includes an amide group having an N—H bond in the formula (2). A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group having an H bond,
The structural unit represented by the formula (2-2) is a carbon that may include an amide group in which R ⁴⁵ is a hydrogen atom and R ²⁹ may have an N—H bond in the formula (2-2). A monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may include an amide group which may have an N-H bond, or R ²⁹ , At least one of R ⁴⁵ includes a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms including an amide group having an N—H bond or a monovalent group having 6 to 12 carbon atoms including an amide group having an N—H bond. May be an aromatic hydrocarbon group.

In an embodiment of the present invention, the structural unit represented by the formula (1) has 1 carbon atom in which R ^1a and R ^1b may include an amide group having no N—H bond in the formula (1). A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may contain a monovalent aliphatic hydrocarbon group of -12 or an amide group having no N-H bond,
The structural unit represented by the formula (2) is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms including an amide group in which R ³ does not have an N—H bond in the formula (2) or A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group having no NH bond,
The structural unit represented by the formula (2-2) has 1 to 12 carbon atoms in which R ²⁹ and R ⁴⁵ may include an amide group having no N—H bond in the formula (2-2). It may be a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may contain an amide group having no N—H bond.

  In an embodiment of the present invention, the block polymer may include a second block having a structural unit derived from a monomer having a polymerizable double bond. The monomer having a polymerizable double bond may be at least one selected from a nonionic water-soluble compound, an anionic water-soluble compound, and a nonionic water-insoluble compound.

  In the embodiment of the present invention, an acidic pigment derivative having no basic group may be further included.

  In an embodiment of the present invention, the pigment dispersion can be used for a column spacer of a liquid crystal display device.

  The second of the present invention relates to a coloring composition comprising the above-mentioned pigment dispersion and a coating film-forming component containing an epoxy group.

  The pigment dispersion according to the present invention has a good dispersion stability, and by using the pigment dispersion, a coloring composition having excellent storage stability even when an epoxy group-containing resin is contained in the coating film forming component is provided. can do.

<Pigment dispersion>
The pigment dispersion according to the present invention includes a pigment, a dispersant, and a solvent. However, those containing quaternary ammonium salts are excluded. The dispersing agent is a block copolymer having a predetermined first block at one end. This block copolymer (hereinafter referred to as “block copolymer A” for convenience) has a linear structure and does not have a basic group. And a 1st block has at least 1 sort (s) selected from the structural unit represented by following formula (1), (2) and (2-2).

(In formula (1), R ^1a and R ^1b are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. And at least one is not a hydrogen atom, a hydrogen atom directly connected to a carbon atom contained in each hydrocarbon group of R ^1a and R ^1b is —C (═O) —NR ^5a R ^5b , —O -C (= O) -NR < ^6a > R < ^6b >, -NR < ⁷ > -C (= O) -NR < ^8a > R < ^8b >, a cyclic amide group, -OH or -COOH, and an aliphatic hydrocarbon group In the case where the number of carbon atoms is 2 to 12, at least one double bond may be included in the carbon-carbon bond, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( = O) -, - C ( = O) -O -, - O-C (= O) -, - C (= O) -NR 9 - ^{-NR 10 -C (= O) -} , - NR 11 -C (= O) -O -, - O-C (= O) -NR 12 - or ^{-NR 13 -C (= O) -NR} 14 - R ^{5a to} R ¹⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ^5a and R ^5b , R ^6a and R ^6b, and R 5 ^8a and ^{R 8b} are not each of the at least one of hydrogen atom, ^{R 7} and ^{R 8a} or ^{R 8b, R 13} and ^{R 14} are each, are connected by a divalent hydrocarbon group having 1 to 4 carbon atoms ring structures In R ^1a and R ^1b , the aliphatic hydrocarbon groups having 1 to 4 carbon atoms may be connected to each other by —O— to form a ring structure.
R ² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

(In formula (2), R ³ may have a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an N—H bond, including an amide group that may have an N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group is represented.
Aliphatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 15a} R 15b, -O-C (= O) -NR 16a R 16b, -NR ¹⁷ —C (═O) —NR ^18a R ^18b , a cyclic amide group, —OH or —COOH may be substituted, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( ═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ¹⁹ —, —NR ²⁰ —C (═O) —, —NR ²¹ -C (= O) -O -, - O-C (= O) -NR 22 - or ^{-NR 23 -C (= O) -NR} 24 - may be replaced. R ^{15a to} R ²⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁷ and R ^18a or R ^18b , R ²³ and R ²⁴ each have 1 to Nitrogen atoms may be connected by a divalent hydrocarbon group of 4 to form a ring structure. In addition, when the aliphatic hydrocarbon group has 2 to 12 carbon atoms, at least one double bond may be included in the carbon-carbon bond.
Aromatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 25a} R 25b, -O-C (= O) -NR 26a R 26b, -NR ²⁷ —C (═O) —NR ^28a R ^28b , a cyclic amide group, —OH or —COOH may be substituted. R ^{25a to} R ^28b each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ²⁷ and R ^28a or R ^28b represent a divalent carbon atom having 1 to 4 carbon atoms. Nitrogen atoms may be linked by a hydrogen group to form a ring structure.
R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

(In formula (2-2), R ²⁹ and R ⁴⁵ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Represents a hydrocarbon group and at least one is not a hydrogen atom.
Aliphatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 31a} R 31b, -O-C (= O) -NR 32a R 32b, -NR ³³ —C (═O) —NR ^34a R ^34b , a cyclic amide group, —OH or —COOH may be substituted, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( ═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ³⁵ —, —NR ³⁶ —C (═O) —, —NR ^37. -C (= O) -O -, - O-C (= O) -NR 38 - or ^{-NR 39 -C (= O) -NR} 40 - may be replaced. R ^{31a to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ³³ and R ^34a or R ^34b , R ³⁹ and R ⁴⁰ , respectively, Nitrogen atoms may be connected by a divalent hydrocarbon group of 4 to form a ring structure. In addition, when the aliphatic hydrocarbon group has 2 to 12 carbon atoms, at least one double bond may be included in the carbon-carbon bond.
Aromatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 41a} R 41b, -O-C (= O) -NR 42a R 42b, -NR ⁴³ —C (═O) —NR ^44a R ^44b , a cyclic amide group, —OH or —COOH may be substituted. R ^{41a to} R ^44b each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ⁴³ and R ^44a or R ^44b are divalent carbon atoms having 1 to 4 carbon atoms. Nitrogen atoms may be linked by a hydrogen group to form a ring structure.
R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

  By using the block polymer A having such a specific structure as a dispersant, the first block located at one end of the block polymer A has affinity with a pigment based on an amide group, and The remainder extending linearly from one block can be stably dispersed in the solvent due to the affinity with the solvent and the effect of steric repulsion, and it is considered that the dispersion stability is good. Moreover, since the block polymer A does not contain a basic group such as an amine, even if an epoxy resin is used as a coating film forming component, it does not react with the block polymer A. This is different from basic groups such as amine, and the nitrogen atom of the amide bond cannot show amide basicity due to electron shortage due to the strong electron withdrawing property of the oxygen atom of C═O. This is considered to be due to the good affinity with the pigment. Furthermore, since the pigment dispersion does not contain a quaternary ammonium salt, it has excellent solvent resistance when a coating film is formed.

The structural unit represented by the formula (1) includes an amide bond directly connected to the carbon atom serving as the main chain in the side chain. Therefore, R ^1a , R ^1b and R ² may or may not contain an amide group. R ^1a and R ^1b are each independently a hydrogen atom or a monovalent aliphatic carbon atom having 1 to 12 carbon atoms from the viewpoint of affinity with a solvent and affinity with a pigment (steric hindrance around an amide group). It is a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least one of them is not a hydrogen atom. That is, (i) one of R ^1a and R ^1b is a hydrogen atom and the other is the predetermined hydrocarbon group, and (ii) both are the predetermined hydrocarbon group. In the case of (ii), as compared with the case of (i), even when moisture is mixed into the pigment dispersion for some reason, the increase in the viscosity of the pigment dispersion tends to be effectively suppressed. The effect of suppressing the viscosity with respect to moisture mixing is the same in the case of the structural units represented by the formulas (2) and (2-2). Further, R ^2, from the viewpoint of the polymerization reactivity of the monomer, a monovalent hydrocarbon group having a hydrogen atom or 1 to 4 carbon atoms.

  The monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms may be linear or branched. When the number of carbon atoms is 2 to 12, at least one double bond may be included in the carbon-carbon bond. Thereby, the UV curability is improved, the hardness of the resist film is improved, and the solvent resistance tends to be improved. The number of double bonds and their sites are not particularly limited. About the number, 1-3 may be suitable from a viewpoint of UV curability and a dispersing agent synthesis | combination. As for the site, the end portion may be preferable from the viewpoint of UV curability.

The monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms may or may not have a substituent. The presence or absence of a substituent can be determined in consideration of the affinity with the pigment, the affinity with the solvent, and the like. As such a substituent, —C (═O) —NR ^5a R ^5b , —O—C (═O) —NR ^6a R ^6b , —NR ⁷ —C (═O) —NR ^8a R ^8b , cyclic Amido group, —OH or —COOH may be mentioned. Examples of the cyclic amide group include an α-lactam group, a β-lactam group, a γ-lactam group, a δ-lactam group, and an ε-caprolactam group. R ^{5a to} R ^8b are each independently preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. This tends to improve the viscosity stability of the dispersion over time. The monovalent hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include linear and branched saturated / unsaturated aliphatic hydrocarbon groups and cyclic saturated / unsaturated aliphatic hydrocarbon groups. Is mentioned. R ⁷ and R ^8a or R ^8b may be connected to each other by a divalent hydrocarbon group having 1 to 4 carbon atoms to form a ring structure. That is, a ring structure is formed by connecting nitrogen atoms to which R ⁷ and R ^8a or R ^8b are bonded via a divalent hydrocarbon group having 1 to 4 carbon atoms. Also good. When it has such a ring structure, the steric hindrance around the amide group is reduced, and the affinity with the pigment tends to be improved. As a C1-C4 bivalent hydrocarbon group which comprises this ring structure, a linear saturated hydrocarbon group etc. are mentioned, for example. Moreover, it is preferable that it connects with the terminal of a linear saturated hydrocarbon group.

Of these monovalent aliphatic hydrocarbon groups having 2 to 12 carbon atoms having these substituents, those that overlap with the case where —CH ₂ — described later is substituted are excluded.

The monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, when the number of carbon atoms is 2 to 12, is —CH ₂ — constituting —O—, —C (═O) —, —C ( = O) -O-, -OC (= O)-, -C (= O) -NR < ⁹ >-, -NR < ¹⁰ > -C (= O)-, -NR < ¹¹ > -C (= O) -O. -, -OC (= O) -NR < ¹² >-or -NR < ¹³ > -C (= O) -NR < ¹⁴ >-may be substituted. When it has such a bond instead of —CH ₂ —, the affinity with the pigment tends to be improved. The presence / absence, type, and number of replacements can be determined in consideration of the affinity with the solvent. R ^{9 to} R ¹⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. This tends to improve the viscosity stability of the dispersion over time. The monovalent hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include linear and branched saturated / unsaturated aliphatic hydrocarbon groups and cyclic saturated / unsaturated aliphatic hydrocarbon groups. Is mentioned. R ¹³ and R ¹⁴ may be connected to each other by a divalent hydrocarbon group having 1 to 4 carbon atoms to form a ring structure. That is, the nitrogen atom to which each of R ¹³ and R ¹⁴ is bonded may be connected via a divalent hydrocarbon group having 1 to 4 carbon atoms to form a ring structure. When it has such a ring structure, the steric hindrance around the amide group is reduced, and the affinity with the pigment tends to be improved. As this C1-C4 bivalent hydrocarbon group, a linear saturated hydrocarbon group etc. are mentioned, for example.

R ^1a and R ^1b may be formed by connecting aliphatic hydrocarbon groups having 1 to 4 carbon atoms with —O—. Examples of such aliphatic hydrocarbon groups include straight-chain saturated hydrocarbon groups. Moreover, it is preferable that the aliphatic hydrocarbon group has an oxygen atom as a linking group at its end.

In the formula (1), specific examples in the case where R ^1a and R ^1b are monovalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms are as follows. However, it is not limited to these specific examples.

Unsubstituted aliphatic hydrocarbon: methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group (including isomers thereof) , Hexyl group (including its isomer), heptyl group (including its isomer), octyl group (including its isomer), nonyl group (including its isomer), decyl group (including its isomer) ), Undecyl group (including its isomer), dodecyl group (including its isomer), etc.
Aliphatic hydrocarbon group having —OH as a substituent: —CH ₂ CH ₂ OH, —CH ₂ CH (OH) —CH ₃ , —CH (CH ₃ ) —CH ₂ OH, —CH ₂ CH ₂ CH ₂ OH _{, -CH 2 CH 2 CH 2 CH} 2 OH, etc.,
Aliphatic hydrocarbon groups having -COOH as a _{substituent: -CH 2 CH 2 CH 2 CH} 2 CH 2 COOH, -CH 2 CH (COOH) -CH 3 or the like,
Aliphatic hydrocarbon group having —C (═O) —NR ^5a R ^5b as a substituent: —CH ₂ CH ₂ —C (═O) —NH—CH ₂ CH ₃ , —CH ₂ CH ₂ —C (= _{O) -N (CH 2 CH 3} ) -CH 2 CH 3 and the like,
Aliphatic hydrocarbon group having a cyclic amide group as a substituent: a group represented by the following formula (3), a group represented by the following formula (4), or a hydrogen atom bonded to a nitrogen atom of the following formula (4) has 1 to 7 carbon atoms A group substituted with an aliphatic hydrocarbon or an aromatic hydrocarbon having 6 to 7 carbon atoms.

The case where at least one of —CH ₂ — constituting the aliphatic hydrocarbon group is replaced with a predetermined bond is as follows. However, it is not limited to these specific examples.

Examples containing —O—: —CH ₂ —O—CH ₃ , —CH ₂ —O—CH ₂ CH ₃ , —CH ₂ —O—CH ₂ CH ₂ CH ₃ , —CH ₂ —O—CH ₂ CH _{2 CH 2 CH 3, -CH 2 -O} -CH 2 CH (CH 3) 2, -CH 2 CH 2 -O-CH 3, -CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 - _{O-CH 2 CH 2 -O-} CH 3, -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 3, -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH _{2 -O-CH 3, -CH 2} CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 3 and the like,
Examples containing —C (═O) —: —C (CH ₃ ) ₂ —CH ₂ —C (═O) —CH ₃ etc.
Examples containing —C (═O) —O—: —CH ₂ —CH ₂ —C (═O) —O—CH ₃ etc.
Examples containing —O—C (═O) —: — (CH ₂ ) ₆ —O—C (═O) —CH═CH ₂ , — (CH ₂ ) ₉ —O—C (═O) —CH═ CH ₂ , a group represented by the following group of formula (5), and the like:
Examples including —C (═O) —NR ⁹ —: A group represented by the following formula (6), a hydrogen atom bonded to each nitrogen atom of the following formula (6), independently in the formula (6) Groups substituted with aliphatic hydrocarbons or aromatic hydrocarbons such that the total carbon number is 12 or less, etc.
Examples containing —NR ¹⁰ —C (═O) —: —CH ₂ —NH—C (═O) —CH═CH ₂ , —CH ₂ CH ₂ —NH—C (═O) —CH═CH ₂ , The hydrogen atom bonded to each nitrogen atom in the following formula (7) and the following formula (7) is substituted with an aliphatic hydrocarbon having 1 to 7 carbon atoms or an aromatic hydrocarbon having 6 to 7 carbon atoms. Group
Examples containing —NR ¹¹ —C (═O) —O—: a group represented by the following group of formula (8), etc.
Examples containing —O—C (═O) —NR ¹² —: groups represented by the following group of formula (9), etc.
Examples including —NR ¹³ —C (═O) —NR ¹⁴ —: groups represented by the following group of formula (10) and the like.

Examples of R ^1a and R ^1b in which aliphatic hydrocarbon groups having 1 to 4 carbon atoms are connected by —O— to form a ring structure are as follows. However, it is not limited to these specific examples. In formula (10-2), in —NR ^1a R ^1b in formula (1), one end of _two —CH ₂ —CH ₂ — is linked by an oxygen atom, and the other end is each a nitrogen atom. The group which couple | bonded and formed the ring structure is shown.

Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthalene group, an indane group, an indene group, and an azulene group. Moreover, the aromatic hydrocarbon group may or may not have a substituent. The presence or absence of a substituent can be determined in consideration of the affinity with the pigment, the affinity with the solvent, and the like. Examples of such a substituent include —C (═O) —NR ^6a R ^6b , —O—C (═O) —NR ^6a R ^6b , —NR ⁷ —C (═O) —NR ^8a R ^8b , cyclic Amido group, —OH or —COOH may be mentioned. Examples of the cyclic amide group include an α-lactam group, a β-lactam group, a γ-lactam group, a δ-lactam group, and an ε-caprolactam group. R ^{5a to} R ^8b are each independently preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. This tends to improve the viscosity stability of the dispersion over time. The monovalent hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include linear and branched saturated / unsaturated aliphatic hydrocarbon groups and cyclic saturated / unsaturated aliphatic hydrocarbon groups. Is mentioned. R ⁷ and R ^8a or R ^8b may be connected to each other by a divalent hydrocarbon group having 1 to 4 carbon atoms to form a ring structure. That is, the nitrogen atom to which each of R ⁷ and R ^8a or R ^8b is bonded may be linked via a divalent hydrocarbon group having 1 to 4 carbon atoms to form a ring structure. . When it has such a ring structure, the steric hindrance around the amide group tends to be small, and the affinity with the pigment tends to be improved. As a C1-C4 bivalent hydrocarbon group which comprises this cyclic structure, a linear saturated hydrocarbon group etc. are mentioned, for example.
Incidentally, the substituent group of the aromatic hydrocarbon group has been described using the same reference numerals R ^5a to R ^8b and the like the above-described substituents of aliphatic hydrocarbons, which can be determined independently.

In the formula (1), specific examples in the case where R ^1a and R ^1b are a predetermined aromatic hydrocarbon group having a substituent are as follows.
An aromatic hydrocarbon group having —OH as a substituent: a group represented by the following formula (11), etc.
An aromatic hydrocarbon group having —COOH as a substituent: a group represented by the following formula (12), etc.
Aromatic hydrocarbon group having —C (═O) —NR ^5a R ^5b as a substituent: a group represented by the following formula (13), a hydrogen atom bonded to a nitrogen atom of the following formula (13) is a methyl group Substituted groups, etc.
An aromatic hydrocarbon group having —O—C (═O) —NR ^6a R ^6b as a substituent: a group represented by the following formula (14), etc.
An aromatic hydrocarbon group having —NR ⁷ —C (═O) —NR ^8a R ^8b as a substituent: a group represented by the following formula (15), etc.

As described above, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. These can be selected in consideration of the affinity with the solvent and the polymerization reactivity of the monomer. The monovalent hydrocarbon group having 1 to 4 carbon atoms may be linear or have a branched chain. Examples of such hydrocarbon groups include a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group.

The structural unit represented by the formula (2) has an amide group that may have an N—H bond. Therefore, R ³ is configured to have an amide group that may have an N—H bond. And from the viewpoint of affinity with the solvent and affinity with the pigment (steric hindrance around the amide group), R ³ is further a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or 6 to 6 carbon atoms. Twelve monovalent aromatic hydrocarbon groups are preferred. That is, as R ³ , in the case of a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, (i) the hydrogen atom directly connected to the aliphatic hydrocarbon group may have an N—H bond. Substituted with an amide group, (ii) the —CH ₂ — group of the aliphatic hydrocarbon group replaced with an amide group which may have an N—H bond, (iii) the aliphatic hydrocarbon In the group, examples in which both the substitution of (i) and the substitution of (ii) are performed can be exemplified. In the case of a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, a hydrogen atom directly connected to the aromatic hydrocarbon group is substituted with an amide group which may have an N—H bond. It can be illustrated. R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms from the same viewpoint as R ² .

The monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms and the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms in R ³ include one or more amide groups that may have an N—H bond. It is the same as R ^1a or R ^1b except that it is configured to include. R ^{5a to} R ^8b in Formula (1) correspond to R ^{15a to} R ^18b in Formula (2), respectively, and similarly correspond to R ^{25a to} R ^28b in Formula (2), respectively. Also, ^R 9 ^{to R 14} in Formula (1) corresponds to the ^R 19 ^{to R 24} in each formula (2). Therefore, R ^{15a to} R ^28b in the formula (2) are based on the assumption that R ³ is configured to include one or more amide groups that may have an N—H bond. Refer to the description of the corresponding part.

R ⁴ corresponds to R ² in formula (1), and for R ⁴ , the description of R ^{2 in} formula (1) is referred to.

The structural unit represented by the formula (2-2) includes an amide bond directly connected to the carbon atom serving as the main chain in the side chain. Therefore, R ²⁹ , R ³⁰ and R ⁴⁵ may or may not contain an amide group. R ²⁹ and R ⁴⁵ are each independently a hydrogen atom or a monovalent aliphatic carbon atom having 1 to 12 carbon atoms from the viewpoint of affinity with a solvent and affinity with a pigment (steric hindrance around an amide group). It is a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and at least one of them is not a hydrogen atom. That is, (i) one of R ²⁹ and R ⁴⁵ is a hydrogen atom, and the other is the predetermined hydrocarbon group, and (ii) both are the predetermined hydrocarbon group. Note that, as described above, in the case of (ii), there is a tendency that a viscosity suppressing effect against moisture mixing into the pigment dispersion is obtained. R ³⁰ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms from the viewpoint of polymerization reactivity of the monomer.

The monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms and the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms in R ²⁹ and R ⁴⁵ are the same as R ^1a or R ^1b . R ^{5a to} R ^8b in Formula (1) respectively correspond to R ^{31a to} R ^34b in Formula (2-2), and similarly correspond to R ^{41a to} R ^44b in Formula (2-2), respectively. Also, ^R 9 ^{to R 14} in Formula (1) corresponds to the ^R 35 ^{to R 40} in each formula (2-2). Therefore, for R ^{31a to} R ^44b in Formula (2-2), refer to the description of the corresponding part in Formula (1).

R ³⁰ corresponds to R ² in formula (1), and for R ³⁰ , the description of R ^{2 in} formula (1) is referred to.

  The first block having at least one selected from the structural units represented by the formulas (1), (2) and (2-2) is, for example, homopolymerizing or copolymerizing monomers capable of forming each structural unit. Can be obtained. Moreover, you may make it copolymerize with the other monomer copolymerizable with the monomer which can form each structural unit in the range which does not affect the effect show | played by a 1st block. That is, the first block includes a homopolymer of the structural unit represented by the formula (1), a homopolymer of the structural unit represented by the formula (2), and a structural unit represented by the formula (2-2). Homopolymer, Formula (1) and (2), Formula (1) and (2-2), Formula (2) and Formula (2-2), or Formula (1), (2) And random or block copolymers of the structural units represented by (2-2) and copolymers of these polymers with other monomers. Among these, the first block is represented by the homopolymer of the structural unit represented by the formula (1), the homopolymer of the structural unit represented by the formula (2), and the formulas (1) and (2). The structural unit random or block copolymer is preferable, and the structural unit homopolymer represented by the formula (1) and the structural unit homopolymer represented by the formula (2) are more preferable.

  The embodiment of the first block having at least one selected from the structural units represented by formulas (1), (2), and (2-2) can be broadly divided into (A) the side chain of the first block. Among them, there are those containing an amide group having an N—H bond and (B) those containing an amide group having no N—H bond. The solvent used for preparing the pigment dispersion is generally an organic solvent. However, even when water is mixed for some reason, an increase in the viscosity of the pigment dispersion is suppressed. Moreover, even when it mixes with a coating-film formation component and prepares a coloring composition, the storage stability is favorable.

The first block containing an amide group having an N—H bond is composed of, for example, those having at least one of the following structural units. Other structural units that can be polymerized with these may be contained within a range that does not affect the function of the first block, but of course are not limited to those containing no basic group such as an amine.
(I) Among the structural units represented by formula (1), one of R ^1a and R ^{1b in} formula (1) is a hydrogen atom, and the other has an N—H bond. A monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms containing a good amide group or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms containing an amide group which may have an N-H bond. thing,
(Ii) Among the structural units represented by formula (2), R ³ in formula (2) is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms including an amide group having an N—H bond, or A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group having an N—H bond;
(Iii) Among the structural units represented by the formula (2-2), R ⁴⁵ in the formula (2-2) may be a hydrogen atom, and R ²⁹ may contain an amide group that may have an N—H bond. A monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may include an amide group which may have an N-H bond;
(Iv) Among the structural units represented by the formula (2-2), at least one of R ²⁹ and R ^{45 in} the formula (2-2) has 1 to 12 carbon atoms including an amide group having an N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including a monovalent aliphatic hydrocarbon group or an amide group having an N—H bond.

As a 1st block containing the amide group which does not have a N-H bond, what has at least 1 sort (s) of the following structural units is comprised, for example. Other structural units that can be polymerized with these may be contained within a range that does not affect the function of the first block, but of course are not limited to those containing no basic group such as an amine.
(I) Among the structural units represented by the formula (1), R ^1a and R ^1b in the formula (1) may contain an amide group that does not have an N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, which may include an aliphatic hydrocarbon group or an amide group having no N—H bond,
(Ii) Among the structural units represented by the formula (2), R ³ in the formula (2) is a monovalent aliphatic hydrocarbon having 1 to 12 carbon atoms including an amide group having no N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, including a group or an amide group having no NH bond,
(Iii) Among the structural units represented by the formula (2-2), R ²⁹ and R ⁴⁵ in the formula (2-2) may contain an amide group having no N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may include 12 monovalent aliphatic hydrocarbon groups or an amide group having no N—H bond.

  Examples of the monomer that can form the structural unit represented by the formulas (1), (2), and (2-2) include an amide bond that may have an N—H bond and a basic group. And a monomer having a polymerizable double bond that is not used. Examples of such monomers include acrylamide monomers, methacrylamide monomers, acrylate ester monomers having amide bonds, methacrylic ester monomers having amide bonds, N-vinylcarboxylic acid amides, and the like. In the following description, “(meth) acryl” is used to mean “acryl” and / or “methacryl” unless otherwise specified.

  Examples of (meth) acrylamide monomers include (meth) acrylamide, N-alkyl (meth) acrylamide, N, N-alkyl (meth) acrylamide, N-alkylalkoxyalkyl (meth) acrylamide, and N, N-alkylalkoxy. Alkyl (meth) acrylamide, N-hydroxyalkyl (meth) acrylamide, N, N-hydroxyalkyl (meth) acrylamide, N-carboxyalkyl (meth) acrylamide, N, N-carboxyalkyl (meth) acrylamide, 4-acryloylmorpholine Etc. More specific examples include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide, N, N-diisopropyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N, N-diisobutoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N, N-dihydroxymethyl (Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dihydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N, N-dihydroxypropyl (meth) acrylamide, N-methyl (meta) Acu Luamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-propyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N- n-butylacrylic (meth) acrylamide, N, N-di (n-butylacrylic) (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N, N-dicyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-di (2-methoxyethyl) (meth) acrylamide, N-phenyl (Meth) acrylamide, N, N-diphenyl (meth) acrylamide, Acetone (meth) acrylamide.

  Examples of (meth) acrylic acid ester monomers include 2- (methacryloyloxyacetamidoethylene) -N, N′-ethyleneurea (MEU), hydroxyethyl methacrylate (HEMA) and 2-isocyanatoethyl methacrylate (MOI). An addition reaction product (HEMA-MOI) (see formula (16) described later), N-ethylcarbamic acid methyl acrylate, and the like can be given.

The N- vinylcarboxamides, for example, general ^formula, include those represented by ^{CHR 30 = CH-NR 45 -CO} -R 29. Specific examples include N-vinylacetamide and N-vinyl-N-alkylacetamide. Examples of N-vinyl-N-alkylacetamide include N-vinyl-N-methylacetamide.

  Examples of other monomers that can be copolymerized with the monomer that can form the structural unit represented by the formulas (1), (2), and (2-2) include, for example, a nonionic non-ionic group that does not have a basic group described below. A water-soluble compound is mentioned, Among these, a vinyl-type monomer is preferable, For example, an alkyl (meth) acrylate, a styrene-type monomer, etc. are mentioned. These copolymerizable compounds can be used singly or in combination of two or more.

  The content of the structural unit (first block) represented by the formula (1) and / or (2) and / or (2-2) in the block copolymer A is not particularly limited, but from the viewpoint of dispersion stability. The amount of the block copolymer A is preferably 10 to 50% by weight, more preferably 25 to 40% by weight. Moreover, the weight ratio in the case of including 2 or more types among the structural units represented by Formula (1), (2) and Formula (2-2) is not particularly limited. For example, when both of the structural units represented by the formulas (1) and (2) are included, the weight ratio between the two (formula (1) / formula (2)) is determined according to the affinity with the pigment. However, 100/0 to 50/50 is preferable from the viewpoint of dispersion stability.

  In the embodiment of the present invention, the block copolymer A constituting the dispersant may have a second block. One end of the second block is coupled to one end of the first block and has a linear structure. The structural unit constituting the second block can be selected in consideration of affinity with a solvent, dispersion stability, steric repulsive force, and the like. Such a structural unit is preferably at least one selected from a structural unit derived from a nonionic water-soluble compound, a structural unit derived from an anionic water-soluble compound, and a unit derived from a nonionic water-insoluble compound. The second block may be a random copolymer or a block copolymer when the structural unit contains two or more kinds of structural units, but is preferably a block polymer from the viewpoint of dispersion stability.

  The nonionic water-soluble unit is a divalent structural unit derived from a nonionic water-soluble compound. The nonionic water-soluble compound is not particularly limited as long as it is a nonionic and water-soluble and polymerizable organic compound, but a nonionic water-soluble organic compound having a hydroxyl group and polymerizable is preferable. The nonionic water-soluble organic compound may have a polymerizable group, and the polymerizable group is preferably a group having a polymerizable double bond, more preferably an alkenyl group, and still more preferably a vinyl group.

  Examples of the polymerizable nonionic water-soluble organic compound having a hydroxyl group include polyalkylene glycol, polyalkylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, and alkylene oxide. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyalkylene glycol include polyalkylene glycols having 2 to 4 carbon atoms in the alkylene chain, such as polyethylene glycol, polypropylene glycol, and polybutylene glycol.

  Examples of the polyalkylene glycol (meth) acrylate include monofunctional or polyfunctional esters of a polyalkylene glycol having an alkylene chain with 2 to 4 carbon atoms and acrylic acid or methacrylic acid, more specifically. Polyethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, phenoxypolyethylene glycol acrylate, polypropylene glycol monomethacrylate, polypropylene glycol diacrylate, and the like.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. The hydroxyalkyl (meth) acrylate which is is mentioned.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.

  The content of the nonionic water-soluble unit in the block copolymer A is preferably 0 to 40% by weight with respect to the total amount of the block copolymer A from the viewpoints of affinity with a solvent, dispersion stability, and the like. Preferably it is 0 to 30% by weight.

  An anionic water-soluble unit is a divalent structural unit derived from an anionic water-soluble compound. The anionic water-soluble compound is not particularly limited as long as it is an anionic and water-soluble organic compound having a polymerizable group, but at least selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. An anionic water-soluble organic acid compound having one acid group (hereinafter sometimes simply referred to as “acid group”) and a polymerizable group in one molecule is preferable. The polymerizable group is preferably a group having a polymerizable double bond, more preferably an alkenyl group, and still more preferably a vinyl group.

  Specific examples of the anionic water-soluble organic acid compound having an acid group and a polymerizable group include a carboxylic acid compound, a sulfonic acid compound, and a phosphoric acid compound. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the carboxylic acid compound include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, fumaric acid, maleic acid, cinnamic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, sorbic acid, α, β -Methyl glutaric acid, maleic anhydride, itaconic anhydride, acrylic anhydride, methacrylic anhydride, and salts thereof.

  Examples of the sulfonic acid compound include vinyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, allyloxybenzene sulfonic acid, methallyl sulfonic acid, (meth) allyloxybenzene sulfonic acid, 2 -Allyloxy-2-hydroxypropanesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 2-methacryloyloxyethanesulfonic acid, salts thereof, and the like.

  Examples of the phosphoric acid compound include 2-methacryloyloxyethyl phosphoric acid, 2-methacryloyloxyethylphenyl phosphoric acid, 10-methacryloyloxydecamethylene phosphoric acid, 4-vinylbenzyl phosphoric acid, pentaacryloyldipentaerythritol phosphoric acid, and These salts and phosphate esters such as 2- (meth) acryloyloxyethyl phosphate, diethyl (vinylphenyl) phosphate, 4-vinylbenzenephosphinic acid diethyl ester, diphenyl-2-methacryloyloxyethyl phosphate, and the like can be mentioned.

  In addition, since a phosphoric acid group can also be a polymerizable group [= P (O) (OH)], phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphate esters such as tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate may also be used as the anionic water-soluble organic acid compound.

  The content of the anionic water-soluble unit in the block copolymer A is preferably 0 to 30% by weight, based on the total amount of the block copolymer A, from the viewpoint of solubility in a developer, dispersion stability, and the like. Preferably it is 0 to 20% by weight.

  The nonionic water-insoluble unit is a divalent structural unit derived from a nonionic water-insoluble compound. Nonionic water-insoluble units are used, for example, to adjust the degree of hydrophilicity of the second block. Moreover, when the hydrophilic property of a nonionic water-insoluble unit is higher, there exists a function which improves the hydrophilic property of a 2nd block. The nonionic water-insoluble compound is not particularly limited as long as it is a nonionic and water-insoluble organic compound having a polymerizable group, but a chain hydrocarbon group, a cyclic hydrocarbon group, an aromatic hydrocarbon group. Nonionic water-insoluble organic compounds having at least one hydrophobic group selected from the group consisting of these groups (hereinafter sometimes simply referred to as “hydrophobic group”) and a polymerizable group in one molecule are preferred. The polymerizable group is preferably a group having a polymerizable double bond, more preferably an alkenyl group, and still more preferably a vinyl group.

  Nonionic water-insoluble organic compounds having a hydrophobic group and a polymerizable group in one molecule include, for example, chain alkyl (meth) acrylates, cycloalkyl (meth) acrylates, aryl (meth) acrylates, styrene compounds, etc. Is mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the chain alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Examples include alkyl (meth) acrylates having 1 to 17 carbon atoms in the alkyl moiety, such as acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. It is done.

Examples of the cycloalkyl (meth) acrylate include cyclopropyl (meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, Examples thereof include cycloalkyl (meth) acrylates having 3 to 10 carbon atoms in the cycloalkyl moiety, such as cyclononyl (meth) acrylate and cyclodecyl (meth) acrylate.
Examples of the aryl (meth) acrylate include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.

  Examples of the styrene compound include styrene, α-methylstyrene, methylstyrene, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, methoxystyrene, chloromethylstyrene, chlorostyrene, and 4-tert. -As a substituent, at least one selected from the group consisting of a chain alkyl group having 1 to 4 carbon atoms, a chain alkoxy group having 1 to 4 carbon atoms, and a halogen atom, such as butylstyrene, vinyl toluene, and vinyl toluene. A styrene compound is mentioned.

  The content of the nonionic water-insoluble unit in the block copolymer A is preferably 30 to 80% by weight, based on the total amount of the block copolymer A, from the viewpoints of affinity with a solvent, dispersion stability, and the like. More preferably, it is 50 to 70% by weight.

  In the block copolymer A, the first block is preferably 10 to 50% by weight, the second block is 50 to 90% by weight, and the total of both is preferably 100% by weight. The second block is a weight ratio (A / B / C) of the unit (A) derived from the nonionic water-soluble compound, the unit (B) derived from the anionic water-soluble compound, and the nonionic water-insoluble compound unit (C). ) Is 0 to 70/0 to 70/30 to 100 with respect to the entire second block, and the total of A, B and C is preferably 100% by weight.

  The block copolymer A can be synthesized using, for example, a known polymerization method such as living (controlled) radical polymerization. The living radical polymerization methods are roughly classified into ATRP (atom transfer radical polymerization) method, RAFT (reversible addition-fragmentation chain transfer polymerization) method, NMP (nitroxide mediated radical polymerization) method, TERP (organic tellurium mediated radical polymerization). Method, RTCP (reversible transfer catalytic polymerization) method, etc., and these may be selected as appropriate.

  The ATRP method uses an organic halide as a polymerization initiator, and a polymerization using a transition metal complex consisting of a metal selected from Group 8, Group 9, Group 10 and Group 11 elements and a ligand as a catalyst. It is a method to do. Examples of the organic halide include monofunctional compounds such as ethyl 2-bromopropionate, butyl 2-bromide propionate, 2-bromopropiononitrile, 2-isobutyronitrile bromide, and the like. -Bifunctional compounds such as diethyl dibromoadipate, dimethyl 2,6-dibromopimelate, diethyl 2,6-dibromopimelate, and polyfunctional compounds such as tris (bromomethyl) benzene can be used. As the transition metal complex, complexes of monovalent and zerovalent copper, divalent ruthenium, divalent iron, divalent nickel and the like can be used. For example, when an organic bromide or a sulfonyl bromide compound is used as a polymerization initiator, a transition metal comprising copper bromide, preferably copper contained in cuprous bromide as a central metal and a ligand such as pentamethyldiethylenetriamine. It is preferable to use the complex as a catalyst.

  The RAFT polymerization method is a method using a thiocarbonylthio compound as a chain transfer agent. As the thiocarbonylthio compound, any compound having a thiocarbonylthio group having a dithioester structure or a trithiocarbonate structure can be used without particular limitation.

  The NMP method is a method in which a nitroxide compound or an alkoxyamine compound derived from a nitroxide compound is used as a regulator for controlling polymerization. Examples of the nitroxide compound include 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the substituent is carbon. The alkyl group of number 1-4 is mentioned. Examples of nitroxide compounds include 2,2,6,6-tetramethyl-1-piperidinyl oxide, 2,2,6,6-tetraethyl-1-piperidinyl oxide, 2,2,6,6-tetramethyl. -4-oxo-1-piperidinyl oxide, 2,2,5,5-tetramethyl-1-pyrrolidinyl oxide and the like, and as an alkoxyamine compound derived from a nitroxide compound, N- (tert-butyl ) -N- (1-diethylphosphono-2,2-dimethylpropyl) -O- (2-carboxylprop-2-yl) hydroxyamine and the like. The nitroxide compound is used in combination with a radical generator. The combination ratio of both is not particularly limited, but may be 0.1 to 10 mol of the radical generator with respect to 1 mol of the nitroxide compound. As the radical generator, general organic peroxides and azo compounds are used.

  The TERP method is a method in which polymerization is performed in the presence of an organic tellurium compound through thermal dissociation of a bond between a tellurium atom and carbon, followed by degenerative chain transfer. Specific examples of the organic tellurium compound include (methylterranylmethyl) benzene, (1-methylterranylethyl) benzene, 1-chloro-4- (1-methylterranylethyl) benzene, 1-trifluoromethyl-4. -(1-methylteranylethyl) benzene, 3,5-bis-trifluoromethyl-1- (1-methylterranylethyl) benzene, 1,2,3,4,5-pentafluoro-6- (1 -Methyl terranyl ethyl) benzene, 2-methyl teranyl propionitrile, (2-methyl teranyl propyl) benzene, methyl 2-methyl teranyl-2-methyl-propionate, ethyl 2-methyl teranyl-2-methyl-propionate, 2 -Methyl teranyl-2-methyl-propionitrile.

  Living radical polymerization is, for example, −100 to 250 ° C., preferably 0 to 200 ° C., more preferably room temperature to 200 ° C., and still more preferably 50 to 150 ° C., without solvent (bulk polymerization) or in a solvent. Can be implemented.

  As the solvent, a solvent inert to the polymerization reaction can be used without any particular limitation. For example, hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon systems such as methylene chloride and chloroform. Solvent, ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohol solvent such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, nitrile solvent such as acetonitrile, propionitrile, benzonitrile, Examples thereof include ester solvents such as ethyl acetate and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, and amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide.

  In order to produce the block copolymer A by the living radical polymerization method, a method of sequentially adding a predetermined amount of a raw material compound as a group of each constituent unit, one polymer block synthesized in advance as a polymer polymerization initiator Examples include a method of polymerizing the other polymer block, a method of polymerizing separately polymer blocks, and the like. In the case of sequential addition of raw material compounds, it is desirable to charge the next raw material compound when the conversion rate of the raw material compound previously charged is 80 to 95%. The conversion rate is obtained by, for example, gas chromatography, nuclear magnetic resonance spectroscopy, gravimetric method, or the like.

  As a method of polymerizing the other polymer block using one polymer block synthesized in advance as a polymer initiator, for example, at a desired time during polymerization of one polymer block, the temperature is once lowered in a living state, There is a method in which the polymerization is stopped, the raw material compound of one polymer block is distilled off under reduced pressure, and then the raw material compound of the other polymer block is added. The same operation may be performed when polymerizing the third and subsequent polymer blocks.

  Living radical polymerization methods are described in, for example, Macromolecules, 1995, 28, 1721-1723; Am. Chem. Soc. 1995, 117, 5614-5615; Chem. Rev. 2001, 101, 3661-3688; Macromolecules, 2000, 33, 4403-4410; Macromolecules, 2006, 39, 8274-8282; Aust. J. Chem. 2005, 58, 379-410; Polymer, 2007, 48, 1-53; HANDBOOK OF RADICAL POLYMERIZATION; Matyjaszewski and TP Davis Ed., Wiley, 2002, p. 661; International Publication No. 2004/014962; JP 2009-256457 A; JP 2007-92014 A; ing.

  As for the molecular weight of the block polymer A, the peak top molecular weight is preferably in the range of 4000 to 40000, more preferably 5000 to 20000, from the viewpoint of dispersion stability. The molecular weight of the block copolymer A can be adjusted by appropriately selecting the type and content of each structural unit, the timing of stopping the polymerization reaction, and the like. In addition, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is preferably 1.05 to 1.7 and more preferably 1.05 to 1.5 from the viewpoint of dispersion stability.

  The acid value and amine value of the block copolymer A are determined by the functional group contained in the block copolymer A and its content. The acid value (acid value when converted to solid content) can be determined, for example, by a method based on DIN EN ISO 2114. The amine value (amine value when converted to solid content) is, for example, DIN 16945, for example. It can obtain | require by the method based on. The acid value of the block copolymer A is not particularly limited, but is preferably 85 mgKOH / g or less, and more preferably 30 mgKOH / g or less. The amine value of the block copolymer A is preferably 1 mgKOH / g or less.

  The content (solid content or active ingredient) of the dispersant in the pigment dispersion is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the pigment from the viewpoint of dispersion stability, optical properties such as OD value and color purity. 5 to 50 parts by weight is more preferable. However, the optimum addition amount of the dispersant may be appropriately adjusted depending on the combination with the type of pigment used. In addition, when using the pigment derivative mentioned later, content of this pigment means the total amount including a pigment derivative.

  The dispersant may contain an additive such as a solvent as long as it does not contain a basic group in addition to the block polymer A.

  As the pigment, for example, various organic pigments and inorganic pigments generally used for column spacer applications can be used. Examples are as follows.

  Black pigments: aniline black, perylene black, anthraquinone black, titanium black, cyanine black, lignin black, lactam black, carbon black (CI pigment black 7) and the like.

Examples of aniline black include C.I. I. Pigment black 1, pigments described in Japanese Patent No. 6018363, pigments described in Japanese Patent No. 5712633, and the like. Examples of perylene black include C.I. I. Pigment Black 31, 32, pigments described in Japanese Patent No. 4980727, Lumogen Black FK4280, Lumogen Black FK4281, manufactured by BASF, Palogen Black S0084, Paliogen Black L0086, and the like. Examples of anthraquinone black include C.I. I. Pigment black 20 and the like. Examples of the lactam black include BASF Black 582, Irgaphor (registered trademark) Black S0100CF, and the like. Examples of carbon black include MA7, MA8, MA100, MA600, MCF-88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44 manufactured by Mitsubishi Chemical Corporation. , # 45, # 47, # 52, # 85, # 95, # 240, # 850, # 900, # 950, # 960, # 970, # 980, # 1000, # 2300, # 2350, # 2600, # 2650,
Monarch (registered trademark) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL99, REGAL99R, REGA15R, RGAL250 ,
Raven (registered trademark) 11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven80, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 Raven1170, Raven1190U, Raven1250, Raven1500, Raven2000, Raven2500U, Raven3500, Raven5000U, Raven5250, Raven5750, Raven7000,
Printex (registered trademark) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex85, Printex85, PrintP85, PrintP85, PrintP85, PrintL80, PrintL80 U, Printex V, Printex G, Special Black (registered trademark) 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Special Black 4 (Registered Trademark) FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black FW255, Color Black S160, Color Black S160, Color 0 Pigments described in JP-A No. 2002-249678, pigments described in JP-A 2007-308582, pigments described in JP-A 2009-120640, pigments described in International Publication No. 2013/129554, etc. Can be mentioned.

  Red organic pigment: C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 31, 32, 38, 41, 48, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49, 52, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58, 60: 1, 63, 64: 1, 68, 81: 1, 83, 88, 89, 95, 112, 114, 119, 122, 123, 129, 136, 144, 146, 147, 149, 150, 164, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 181, 183, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 211, 213, 2 4, 216, 220, 221, 224, 226, 237, 238, 239, 242, 245, 247, 248, 251, 253, 254, 255, 256, 257, 258, 260, 262, 263, 264, 266, 268, 269, 270, 271, 272, 279.

  Blue organic pigment: C.I. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17: 1, 24, 24: 1, 25, 26, 56, 60, 61, 62, 63, 75, 79, 80 etc.

  Green organic pigment: C.I. I. Pigment Green 1, 4, 7, 8, 10, 36, etc.

  Purple organic pigment: C.I. I. Pigment violet 1, 2, 3, 3: 1, 3: 3, 5: 1, 13, 17, 19, 23, 25, 27, 29, 31, 32, 36, 37, 38, 42, 50, and the like.

  Yellow organic pigment: C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 24, 49, 55, 60, 61, 61: 1, 62, 63, 65, 73, 74, 75, 77, 81, 83, 87, 93, 94, 95, 97, 98, 99, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 120, 123, 124, 126, 127, 128, 129, 130, 133, 138, 139, 150, 151, 152, 153, 154, 155, 165, 167, 168, 169, 170, 172, 173, 174, 175, 176, 179, 180, 181, 182, 183, 185, 191, 191-1, 193, 194, 199, 205, 206, 209, 2 9: 1,212,213,214,215,219, and the like.

  Orange organic pigment: C.I. I. Pigment Orange 1, 2, 3, 4, 5, 13, 15, 16, 17, 19, 24, 31, 34, 36, 38, 40, 43, 46, 48, 49, 51, 60, 61, 62, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 81 etc.

  Brown organic pigment: C.I. I. Pigment Brown 5, 23, 25, 32, 41, 42, etc.

  As the pigment, the above-mentioned pigments can be used alone or in combination of two or more. For example, in a column spacer application, a black organic pigment and other colored organic pigments can be used in combination.

  In the embodiment of the present invention, the pigment content is preferably 8 to 25% by weight and more preferably 10 to 20% by weight from the viewpoint of optical properties such as dispersion stability and OD value. In addition, when using the pigment derivative mentioned later, content of a pigment means the total amount including a pigment derivative.

  The particle diameter of the pigment can be appropriately determined according to the application and the like, and those having an average primary particle diameter, that is, an average primary particle diameter of 20 to 200 nm can be preferably used. For example, in the use of a column spacer or a black matrix, the average primary particle diameter is more preferably 20 to 80 nm from the viewpoint of obtaining a higher OD value when forming a coating film. The average primary particle diameter can be calculated as, for example, the arithmetic average of the maximum widths of a plurality of (for example, 50) primary particles during imaging with a transmission electron microscope (TEM).

  In the embodiment of the present invention, depending on the type of pigment, milling may be performed in advance from the viewpoint of adjusting the average particle diameter. The milling treatment can be performed according to a conventional method depending on the type of organic pigment. Examples of such a milling process include a solvent salt milling method.

  In the embodiment of the present invention, in addition to the above-described dispersant, a pigment derivative may be used as a dispersion aid in order to disperse the pigment more stably in the pigment dispersion. When a pigment derivative is used, a part having affinity with the dispersant, or for example, a pigment derivative into which a polar group is introduced is adsorbed on the surface of each organic pigment, and this can be an adsorption point of the dispersant. In that case, since the dispersant can be present on the pigment surface via the pigment derivative, the pigment can be more stably dispersed in the pigment dispersion as fine particles. Moreover, the reaggregation can be prevented more effectively. However, as described above, the characteristics of the liquid crystal cell may be affected depending on the characteristics of the pigment and the introduced functional group. Therefore, when a pigment derivative is used, it is desirable to determine the type and amount used in consideration of this point and dispersibility.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton and an acidic group or aromatic group is introduced as a substituent in the side chain. Among these, from the viewpoint of adsorptivity with the amide group of the dispersant, a compound into which an acidic group is introduced is preferable. However, it is necessary not to contain a basic group. That is, an acidic pigment derivative having no basic group is preferable. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments and dioxazine pigments. In addition, the host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not generally called pigments.

  Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, JP 2007-186681, JP 2003-167112, JP 2013-199470. Etc. can be used. Specifically, for example, pigment derivatives I to VIII described in Examples described later are included.

  When the pigment derivative is used, the content (solid content) of the pigment derivative in the pigment dispersion is preferably 2 to 15 parts by weight with respect to 100 parts by weight of the pigment from the viewpoint of dispersion stability, and 5 to 10 parts by weight. Is more preferable. However, the optimum addition amount of the pigment derivative may be appropriately adjusted depending on the combination with the pigment to be used and the type of dispersant, the influence on the characteristics of the liquid crystal cell, and the like. Incidentally, “100 parts by weight of pigment” means an amount not containing a pigment derivative.

  In the embodiment of the present invention, from the viewpoint of further improving the dispersibility of the pigment and the like in the pigment dispersion and the coloring composition, a dispersion resin may be used as a dispersion aid in addition to the above-described dispersant. Such a dispersion resin is particularly preferably used when the coating film forming component used in the coloring composition to be described later is a polymerizable component, particularly a photopolymerizable component. Examples of such a dispersion resin include alkali-soluble resins described later. The dispersion resin may be the same type of resin as the alkali-soluble resin used in the coloring composition, or may be a different type of resin. The content of the dispersion resin is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the pigment. In addition, when using a pigment derivative, content of a pigment means the total amount including a pigment derivative.

  The solvent can be appropriately selected according to the type of coating film forming component described later, for example, various organic materials such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic. A solvent is mentioned. Among these, from the viewpoint of coating film forming property, an organic solvent selected from aromatic, ketone, ester, and glycol ether is preferable. Only one organic solvent may be used, or two or more organic solvents may be combined.

  Examples of the aromatic organic solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

  Examples of the ketone organic solvent include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, isophorone, acetophenone, and cyclohexanone.

  Examples of the ester organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, ethyl glycol acetate, propylene glycol monomethyl ether acetate (PMA), propylene Glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxypro Pionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, 1,3-butylene glycol diacetate, etc. That.

Examples of the glycol ether organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso- Propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene Recall monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di Water-soluble glycol ethers such as propylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether,
Ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol-n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol propyl ether, Examples include water-insoluble glycol ethers such as propylene glycol methyl ether propionate.

Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol, isopropanol,
Ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene Glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol Glycerin, mesoerythritol, pentaerythritol and the like.

  Examples of the aliphatic organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

  When used for the preparation of the coloring composition described later, the content of the solvent can be added so that the solid content concentration including the pigment and the like is 50 to 85% by weight from the viewpoint of handleability.

  In the embodiment of the pigment dispersion of the present invention, other additives may be included in addition to the components described above.

  When water is mixed in the pigment dispersion, the water content is desirably 2.0% by weight or less based on the entire pigment dispersion.

  The pigment dispersion can be obtained, for example, by adding the above-described components to a known disperser such as a bead mill, a sand mill, or a disper and dispersing them. The method of adding each component is not particularly limited, and a mixture obtained by mixing the components at the same time may be dispersed. Also, when using multiple types of pigments, each pigment and solvent mixed with a dispersant and / or other optional components are dispersed to prepare a pigment dispersion for each pigment, and these pigment dispersions are mixed. Then, it may be dispersed again. Other methods may be used.

  The average particle diameter of the particles dispersed in the pigment dispersion obtained as described above (hereinafter sometimes referred to as “dispersion average particle diameter”) is not particularly limited, but is generally 30 to 300 nm. Those that are can be preferably used. For example, in the use of a column spacer or a black matrix, the dispersion average particle diameter is more preferably 30 to 150 nm from the viewpoint of the surface smoothness of the coating film. The dispersion average particle size can be measured by, for example, a particle size measuring machine. Moreover, as a particle size measuring machine, Otsuka Electronics Co., Ltd. make, FPAR-1000, etc. are mentioned.

<Coloring composition>
The coloring composition which concerns on this invention contains the coating-film formation component containing a pigment dispersion and an epoxy group. As an embodiment of this pigment dispersion, the above-mentioned one is used. By using such a pigment dispersion, a coating film-forming component containing an epoxy group, a pigment, a dispersant and the like are stably dispersed in a colored composition and contain a conventional basic group. Compared with the dispersant, changes in physical properties of the coating film forming component can be greatly suppressed.

  As a coating film-forming component containing an epoxy group, it contains an epoxy group, has good mechanical properties such as compression displacement and solvent resistance, and suppresses the influence on the properties of the liquid crystal cell, enabling the formation of a coating film. There is no particular limitation as long as it is a component. The polymerizable component preferably contains a photopolymerizable component because it is easy to perform patterning by development (negative development). Accordingly, examples of the coating film forming component include a resin containing an epoxy group and a photopolymerizable component. In this case, the ratio (A / B) of the resin (A) containing an epoxy group and the photopolymerizable component (B) can be appropriately determined according to the use or the like.

  Examples of the resin containing an epoxy group include an epoxy resin having an epoxy group at the terminal. Such epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, cyclic aliphatic type epoxy resin, long chain aliphatic type epoxy resin, glycidyl ester type. An epoxy resin, a glycidylamine type epoxy resin, a biphenyl type epoxy resin, etc. are mentioned. These resins may be used alone or in combination of two or more. Such an epoxy resin is an oligomer having a molecular weight of about 100 to 10,000. Therefore, generally, a cured resin can be obtained by curing in combination with various curing agents depending on the application.

  The curing agent used for curing the epoxy resin may be either a polyaddition type or a catalyst type (addition polymerization type). The polyaddition type may be any of basic type, acidic type and neutral type as long as it has active hydrogen. Examples of the basic type include a primary amine, a secondary amine, and a polyamine (polyamide). Examples of the primary amine and the secondary amine include aliphatic polyamines and aromatic polyamines. Examples of the acidic type include polycarboxylic acid, polycarboxylic acid anhydride, and phenols. Examples of the neutral type include polymercaptans. Examples of the catalyst type include an anionic polymerization type and a cationic polymerization type. Examples of the anionic polymerization type include tertiary amine and imidazole. Examples of the cationic polymerization type include a Lewis acid complex. However, from the viewpoint of storage stability, a heat curable type or a UV curable type is preferable.

  In order to modify the properties of the cured resin of the epoxy resin, additives can be added as necessary. Examples of such a modifier include a diluent and a leveling agent.

  The photopolymerizable component contains at least one photopolymerizable compound. The photopolymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The photopolymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. As specific examples of these addition polymerizable compounds, those described in JP-A-2009-179789 can be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final coloring composition.
For example, it is selected from the following viewpoint. From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these.

  In addition, addition-polymerizable compounds are also compatible with other components (for example, epoxy group-containing resins, alkali-soluble resins, photopolymerization initiators, colorants (pigments), etc.) in the coloring composition. The selection and use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination.

  In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like. The addition polymerizable compound is preferably contained in an amount of 5 to 70% by weight, more preferably 10 to 60% by weight, based on the nonvolatile components in the colored composition. These may be used alone or in combination of two or more. In addition, as for the method of using the addition polymerizable compound, an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, and the like.

  The photopolymerizable component can contain a photopolymerization initiator. As photopolymerization initiators, for example, acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, oxadiazole, coumarin), acridine, biimidazole, For example, oxime ester type. Specific examples of these photopolymerization initiators include those described in JP2009-179789A.

  As content in the coloring composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of a black coating film formation composition, More preferably, 0.5-5. 0% by mass. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well to form a film with good strength.

  In the embodiment of the colored composition according to the present invention, when a photopolymerizable component is included, an alkali-soluble resin may be contained in addition to the pigment dispersion and the photopolymerizable component described above.

  When the coloring composition contains an alkali-soluble resin, for example, in the production of a column spacer by a photolithography process, when the coloring composition is applied to pattern formation, the pattern formability can be further improved.

  As such an alkali-soluble resin, for example, those described in JP2009-179789A can be used. Briefly, the alkali-soluble resin is, for example, a linear organic high molecular polymer having at least 1 in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Having a group that promotes alkali solubility (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  Suitable examples of the alkali-soluble resin include a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

  Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

  Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _{2 = CXY, CH 2 = C} (X) (COOZ) ( wherein, X represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, Y represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, Z represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms).

  These other copolymerizable monomers may be used alone or in combination of two or more.

  The weight average molecular weight of the alkali-soluble resin is preferably 5000 to 50000 from the viewpoint of developability.

Various alkali-soluble resins are commercially available, and specific examples thereof are as follows, but are not limited thereto.
Showa Polymer Co., Ltd .: Lipoxy SPC-2000,
Mitsubishi Rayon Co., Ltd .: Dial NR series,
Diamond hamrock Co. Ltd .. , Manufactured by: Photomer 6173 (COOH-containing Polyurethane acrylic oligomer),
Osaka Organic Chemical Industry Co., Ltd .: Biscote R-264, KS resist 106, SOP-005,
Daicel Chemical Industries, Ltd .: Cyclomer P series, Plaxel CF200 series,
Daicel UCB Corporation: Ebecryl 3800,

  The content of the alkali-soluble resin in the colored composition is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, particularly preferably 3 to 3% by weight in the total solid content of the colored composition. 12% by weight. When it is contained as a dispersing resin in the pigment dispersion, it is the total amount.

  In the embodiment of the coloring composition according to the present invention, when a photopolymerizable component is included, a solvent may be added as necessary. It can prepare suitably by adding a solvent.

Such solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, etc .; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as toluene and xylene.
A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the solvent in the colored composition is such that the total solid content (nonvolatile component) in the colored composition is 15 to 50% by weight in consideration of the type and content of the solvent in the pigment dispersion. It is preferable that it is contained in.

  Also when using a polymer as a coating-film formation component, you may add a solvent similarly to the case where a photopolymerizable component is used. As such a solvent, what can be used with the above-mentioned pigment dispersion and what can be used with a photopolymerizable component can be used.

  Also in this case, the content of the solvent in the colored composition is 15 to 50% by weight of the total solid content (nonvolatile component) in the colored composition in consideration of the type and content of the solvent in the pigment dispersion. % Is preferably included.

  In the embodiment of the coloring composition according to the present invention, if necessary, a dispersion aid, a sensitizer (sensitizing dye), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, Various additives such as a surfactant, an adhesion promoter, an antioxidant, an aggregation inhibitor, and a surface conditioner (leveling agent) may be added. When it is contained in the pigment dispersion, the addition amount may be adjusted.

  When water is mixed in the coloring composition, the water content is desirably 2.0% by weight or less based on the whole coloring composition.

  The coloring composition can be obtained by adding a coating film forming component and optional components to be added to the pigment dispersion, and stirring with a disper or the like.

  The colored composition according to the present invention has a good storage stability compared to a composition containing a conventional dispersant having a basic group, the reaction with the epoxy group contained in the coating film-forming component is suppressed. is there. Moreover, since it does not contain a quaternary ammonium salt, a coating film having excellent solvent resistance can be formed. Such a colored composition is particularly suitable for use as a column spacer for flat panels used in liquid crystal display devices, for example. In addition, it is also suitable as a black matrix for a color filter of an image display device.

  The following examples illustrate the invention more specifically.

Production Example 1 Production of Dispersant I 212.3 parts by weight of methyl methacrylate (MMA), N- (tert-butyl) -N- (1-diethylphosphono-2,2-dimethylpropyl) -O- (2 -Carboxyprop-2-yl) hydroxyamine (manufactured by Arkema, product name BlocBuilder MA) 15 parts by weight, propylene glycol monomethyl ether acetate (PMA) 90 parts by weight, propylene glycol monomethyl ether (PM) 45 parts by weight The mixture was charged into a steel separable flask, and the system was heated to 125 ° C. in an oil bath while nitrogen bubbling and stirring were performed.

  Next, 206.0 parts by weight of butyl methacrylate (BMA), 80 parts by weight of PMA, and 40 parts by weight of PM were charged into the flask, and then reacted at 125 ° C. for 4 hours with nitrogen bubbling and stirring.

  Next, 211.7 parts by weight of N-isopropylacrylamide (NIPAM), 80 parts by weight of PMA, and 40 parts by weight of PM were put into the flask, and reacted at 125 ° C. for 4 hours with nitrogen bubbling and stirring.

  Next, the temperature inside the system was raised to 210 ° C., the pressure inside the system was reduced to 2.0 kPa, and the solvent was distilled off to obtain a block copolymer I. The solid content of the reaction mixture was 40% by weight. When the obtained block copolymer I was measured by GPC, the peak top molecular weight was 9800, and Mw / Mn was 1.20. The acid value was 0 mgKOH / g.

In the block copolymer I thus obtained, block I-1 having a structural unit derived from MMA and block I-2 having a structural unit derived from BMA were linked at one end of each. A structural unit derived from NIPAM having a linear second block and linked to the other end of block I-2 (one of R ^1a and R ^1b in formula (1) is a hydrogen atom and the other is − A first block having a block I-3 having CH (CH ₃ ) ₂ , R ² is a hydrogen atom. That is, the block copolymer I is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer I does not have a basic group. The weight ratio (block I-1 / block I-2 / block I-3) of each block of the block copolymer I is 33.7 / 32.7 / 33.6. Block copolymer I was used as dispersant I.

(Production Example 2) Production of Dispersant II MMA 195.9 parts by weight, N- (tert-butyl) -N- (1-diethylphosphono-2,2-dimethylpropyl) -O- (2-carboxylprop-2 -Yl) 15 parts by weight of hydroxyamine, 80 parts by weight of PMA, and 40 parts by weight of PM are charged into a 2 L stainless steel separable flask, and the system is heated to 125 ° C. in an oil bath while bubbling and stirring with nitrogen. The reaction was allowed to proceed for 4 hours after the temperature was over.

  Next, 190.9 parts by weight of BMA, 70 parts by weight of PMA, and 35 parts by weight of PM were added to the flask, followed by reaction at 125 ° C. for 4 hours while nitrogen bubbling and stirring.

  Next, 31.5 parts by weight of methacrylic acid (MAA), 20 parts by weight of PMA, and 10 parts by weight of PM were put into the flask, and subsequently reacted at 125 ° C. for 4 hours with nitrogen bubbling and stirring.

  Next, 211.7 parts by weight of NIPAM, 80 parts by weight of PMA, and 40 parts by weight of PMA were added to the flask, and then reacted at 125 ° C. for 4 hours with nitrogen bubbling and stirring.

  Next, the temperature inside the system was raised to 210 ° C., the pressure inside the system was reduced to 2.0 kPa, and the solvent was distilled off to obtain a block copolymer II. The solid content of the reaction mixture was 36% by weight. When the obtained block copolymer II was measured by GPC, the peak top molecular weight was 10200 and Mw / Mn was 1.25. The acid value was 8.3 mgKOH / g.

  In the block copolymer II thus obtained, block II-1 having a structural unit derived from MMA and block II-2 having a structural unit derived from BMA are linked at one end of each. The block II-3 having a structural unit derived from MAA at the other end of the block II-2 has a linear second block linked at one end and is linked to the other end of the block II-3 A first block having a block II-4 having a structural unit derived from NIPAM. That is, the block copolymer II is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer II does not have a basic group. The weight ratio of each block of the block copolymer II (Block II-1 / Block II-2 / Block II-3 / Block II-4) was 31.1 / 30.3 / 5.0 / 33.6. is there. Block copolymer II was used as dispersant II.

Production Example 3 Production of Dispersant III A block copolymer III was obtained in the same manner as in Production Example 1 except that N-isobutoxymethylacrylamide (IBMA) (manufactured by MCC Unitech) was used instead of NIPAM. It was. The solid content of the reaction mixture was 38% by weight. When the obtained block copolymer III was measured by GPC, the peak top molecular weight was 8200, and Mw / Mn was 1.18. The acid value was 0 mgKOH / g. The block copolymer III is a linear second block in which a block III-1 having a structural unit derived from MMA and a block III-2 having a structural unit derived from BMA are connected to each other at one end. And one of R ^1a and R ^1b in Formula (1) is a hydrogen atom and the other is —CH ₂ —O—CH _2. A first block having a block III-3 having —CH (CH ₃ ) ₂ , R ² is a hydrogen atom. That is, the block copolymer III is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer III does not have a basic group. The weight ratio (block III-1 / block III-2 / block III-3) of each block of the block copolymer III is 33.7 / 32.7 / 33.6. Block copolymer III was used as dispersant III.

Production Example 4 Production of Dispersant IV A block copolymer IV was obtained in the same manner as in Production Example 1 except that hydroxyethylacrylamide (HEAA) (manufactured by KJ Chemicals) was used instead of NIPAM. The solid content of the reaction mixture was 40% by weight. When the obtained block copolymer IV was measured by GPC, the peak top molecular weight was 9500, and Mw / Mn was 1.25. The acid value was 0 mgKOH / g. The block copolymer IV is a linear second block in which a block IV-1 having a structural unit derived from MMA and a block IV-2 having a structural unit derived from BMA are connected to each other at one end. And a structural unit derived from HEAA linked to the other end of the block IV-2 (one of R ^1a and R ^1b in the formula (1) is a hydrogen atom and the other is —CH ₂ —CH ₂ OH, R ² is a hydrogen atom.) And has a first block having a block IV-3. That is, the block copolymer IV is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer I does not have a basic group. The weight ratio (block IV-1 / block IV-2 / block IV-3) of each block of the block copolymer IV is 33.7 / 32.7 / 33.6. Block copolymer IV was used as dispersant IV.

(Production Example 5) Production of Dispersant V Production Example 1 except that 2- (methacryloyloxyacetamidoethylene) -N, N′-ethyleneurea (MEU) (manufactured by MCC Unitech) was used instead of NIPAM. Similarly, a block copolymer V was obtained. The solid content of the reaction mixture was 42% by weight. When the obtained block copolymer V was measured by GPC, the peak top molecular weight was 6900 and Mw / Mn was 1.34. The acid value was 0 mgKOH / g. The block copolymer V is a linear second block in which a block V-1 having a structural unit derived from MMA and a block V-2 having a structural unit derived from BMA are connected to each other at one end. And a structural unit derived from MEU linked to the other end of the block V-2 (R ³ in the formula (2) is —CH ₂ —CO—NH—CH ₂ —CH ₂ —NX—CO—NHY— , Wherein X and Y are linked by —CH ₂ —CH ₂ — to form a ring structure (see formula (6) above) and R ₄ is —CH ₃ ). 1 has a first block. That is, the block copolymer V is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer V does not have a basic group. The weight ratio (block V-1 / block V-2 / block V-3) of each block of the block copolymer V is 33.7 / 32.7 / 33.6. Block copolymer V was used as dispersant V.

(Production Example 6) Production of Dispersant VI 212.3 parts by weight of MMA, N- (tert-butyl) -N- (1-diethylphosphono-2,2-dimethylpropyl) -O- (2-carboxylprop-2 -Yl) 15 parts by weight of hydroxyamine, 90 parts by weight of PMA, and 45 parts by weight of PMA were charged into a 2 L stainless steel separable flask, and the system was heated to 125 ° C. in an oil bath while nitrogen bubbling and stirring were performed. The reaction was allowed to proceed for 4 hours after the temperature was over.

  Next, 206.0 parts by weight of BMA, 80 parts by weight of PMA, and 40 parts by weight of PMA were charged into the flask, and then reacted at 125 ° C. for 4 hours with nitrogen bubbling and stirring.

  Next, 96.5 parts by weight of 2-hydroxyethyl methacrylate (HEMA) (manufactured by Nippon Shokubai Co., Ltd.), 80 parts by weight of PMA, and 40 parts by weight of PM are charged into the flask, and subsequently reacted at 125 ° C. for 4 hours with nitrogen bubbling and stirring. I let you. When a small amount of the internal volume was sampled and GPC measurement was performed, the peak top molecular weight was 9200, and Mw / Mn was 1.21.

  Next, 10 parts by weight of dibutylhydroxytoluene as a polymerization inhibitor, 115.2 parts by weight of 2-isocyanatoethyl methacrylate (MOI) (manufactured by Showa Denko KK, Karenz MOI (registered trademark)), 30 parts by weight of PMA, 20 parts by weight of PM Was put into a flask and reacted at 80 ° C. for 4 hours with nitrogen bubbling and stirring. The contents were sampled and GPC measurement was performed.

  Next, the temperature inside the system was raised to 210 ° C., the pressure inside the system was reduced to 2.0 kPa, and the solvent was distilled off to obtain a block polymer VI. The solid content of the reaction mixture was 40% by weight. When the obtained block polymer VI was measured by GPC, the peak top molecular weight was 12800 and Mw / Mn was 1.40. The acid value was 0 mgKOH / g.

In the block copolymer VI thus obtained, the block VI-1 having a structural unit derived from MMA and the block VI-2 having a structural unit derived from BMA were linked at one end of each. A structural unit (R in formula (2) derived from an addition reaction product of HEMA and MOI (see formula (16) below)) having a linear second block and linked to the other end of block VI-2 ³ is —CH ₂ —CH ₂ —O—C (═O) —NH—CH ₂ —CH ₂ —O—C (═O) —C (CH ₃ ) ═CH ₂ , and R ⁴ is —CH _3. A first block having a block VI-3. That is, the block copolymer VI is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer VI does not have a basic group. The weight ratio (block VI-1 / block VI-2 / block VI-3) of each block of the block copolymer VI is 33.7 / 32.7 / 33.6. Block copolymer VI was used as dispersant VI.

  Table 1 shows the structures and the like of the dispersants I to VI. In Table 1, “HEMA-MOI” represents an addition reaction product of HEMA and MOI.

(Production Example 7) Production of pigment derivative I In 200 parts by weight of concentrated sulfuric acid (98%), C.I. I. 15 parts by weight of Pigment Red 255, 1.6 parts by weight of paraformaldehyde, and 8.4 parts by weight of 4-aminophthalimide were added and reacted at 85 ° C. for 5 hours. Next, this solution was added to 1 L of ice water, filtered and washed with water to introduce (4-aminophthalimidomethyl) -C. I. 19.5 parts by weight of CI Pigment Red 255 were obtained.

  Next, (4-aminophthalimidomethyl) -C. I. Pigment Red 255 (10 parts by weight) was dispersed in 100 parts of water, 3.6 parts by weight of cyanuric chloride reacting with one amino group was added, and the mixture was reacted at 30 ° C. for 1 hour. Next, 3.4 parts by weight of orthotanic acid was added, and the mixture was reacted at 80 ° C. for 2 hours to hydrolyze the remaining one Cl, and 15.2 parts by weight of pigment derivative I represented by the following formula (17) was added. Obtained. When elemental analysis and mass spectrometry of the pigment derivative I were performed, n = 0.6.

Production Example 8 Production of Pigment Derivative II Using the same method as in Production Example 7, C.I. I. Pigment Red 177 derivative into which one 4-aminophthalimidomethyl group was introduced was prepared using Pigment Red 177 instead of Pigment Red 255.

  Next, 10 parts by weight of Pigment Red 177 derivative introduced with one 4-aminophthalimidomethyl group is dispersed in 100 parts by weight of water, and 3.0 parts by weight of cyanuric chloride in an amount to react with one amino group is added. And reacted at 10 ° C. for 1 hour. Next, 2.8 parts by weight of alternic acid is added and reacted at 90 ° C. for 1 hour to hydrolyze the remaining 1 Cl, and 14.3 parts by weight of pigment derivative II represented by the following formula (18) is added. Obtained. When elemental analysis and mass spectrometry of Pigment Derivative II were performed, n = 1.

Production Example 9 Production of Pigment Derivative III Using the same method as in Production Example 7, C.I. I. Using dimethylquinacridone instead of CI Pigment Red 255, a dimethylquinacridone derivative into which one 4-aminophthalimidomethyl group was introduced was prepared.

  Next, 10 parts by weight of (4-aminophthalimidomethyl) -dimethylquinacridone is dispersed in 100 parts by weight of water, and 3.6 parts by weight of cyanuric chloride reacting with one amino group is added, followed by reaction at 30 ° C. for 1 hour. I let you. Next, 3.4 parts by weight of orthotanic acid was added and reacted at 80 ° C. for 2 hours to hydrolyze the remaining 1 Cl, and 15.2 parts by weight of pigment derivative III represented by the following formula (19) was added. Obtained. As a result of elemental analysis and mass spectrometry of the pigment derivative III, the ratio of the derivative of n = 1 and the derivative of n = 2 in the formula (19) among the components in the produced pigment derivative III was 1: 1. Moreover, almost no derivative with n = 3 or more was produced.

Production Example 10 Production of Pigment Derivative IV C. was replaced with dimethylquinacridone. I. A pigment derivative IV represented by the following formula (20) was obtained in the same manner as in Production Example 9 except that CI Pigment Orange 43 was used.

(Production Example 11) Production of pigment derivative V C.I. I. 20 parts by weight of Pigment Yellow 138 (manufactured by BASF, Paliotol Gelb K0961HD) and 98 parts by weight of sulfuric acid and 300 parts by weight were placed in a 500 ml separable flask and reacted at 120 ° C. for 5 hours to obtain a sulfonated product of a phthalimidoquinophthalone compound. . The reaction mixture was poured into 3000 parts of water while stirring to precipitate a sulfonated product of a phthalimidoquinophthalone compound, stirred for 30 minutes, and then filtered and washed with water three times. The obtained wet cake was washed with 300 parts by weight of 1% dilute sulfuric acid, filtered and washed with water. It dried in the hot air dryer and obtained the pigment derivative V shown by following formula (21) of 54 weight part.
The obtained pigment derivative V was subjected to mass spectrometry using a liquid chromatography-mass spectrometer “LC / MS” (Electro Spray Ionization) manufactured by Hewlett-Packard Co. As a result, m / z 733 [M−H] ⁻ was detected. . When elemental analysis and mass spectrometry of the pigment derivative V were performed, p = 0.8.

(Production Example 12) Production of Pigment Derivative VI 18.3 parts by weight of ortanyl acid (2-aminobenzenesulfonic acid) reacting with 18.4 parts by weight of cyanuric chloride and one chlorine atom of cyanuric chloride in 100 parts by weight of water The mixture was reacted at 10 ° C. for 1 hour. To the obtained reaction product, 16.6 parts by weight of 3-amino-4-methoxybenzamide in an amount capable of reacting with two chlorine atoms of the reaction product was added and reacted at 85 ° C. for 1 hour. The obtained reaction product was collected by filtration, and the resulting residue was washed with water, and then left standing in a constant temperature bath at 100 ° C. overnight to dry, and 32.5 parts by weight of pigment derivative VI represented by the following formula (22) Got.
In AXIMA CFR plus type matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (manufactured by Shimadzu Corporation), α-cyano-4-hydroxycinnamic acid (CHCA) as a matrix in positive ion mode, The molecular ion peak of pigment derivative VI was measured. As a result, a peak was observed at m / z = 582.

(Production Example 13) Production of Pigment Derivative VII 17.3 parts by weight of ortanyl acid (2-aminobenzenesulfonic acid) reacting with 18.4 parts by weight of cyanuric chloride and one chlorine atom of cyanuric chloride in 100 parts by weight of water The mixture was reacted at 10 ° C. for 1 hour. To the obtained reaction product, 29.8 parts by weight of 5-amino-2-benzimidazolinone in an amount capable of reacting with two chlorine atoms of the reaction product was added and reacted at 85 ° C. for 1 hour. The obtained reaction product was collected by filtration, and the obtained residue was washed with water, and then left to stand overnight in a constant temperature bath at 100 ° C. and dried, and 44.7 wt.% Of pigment derivative VII represented by the following formula (23) Got a part. In the same manner as in Production Example 12, the molecular ion peak of pigment derivative VII was measured. As a result, a peak was observed at m / z = 546.

Production Example 14 Production of Pigment Derivative VIII A 500 ml four-necked flask was set in an oil bath, PM 200 g, tetrachlorophthalic anhydride 41.95 g (150 mmol), O-phosphorylethanolamine 20.70 g (150 mmol), 1, 4-Diazabicyclo [2,2,2] -octane (33.65 g, 300 mmol) was added, and a cooling tube was installed at the top, and the mixture was heated to reflux for 6 hours while stirring with a magnetic stirrer. After cooling to room temperature, the contents were filtered with Nutsche, and the residue was washed with PM. The residue was redispersed in 1.5 L methanol for 30 minutes, and then 300 g of 35% hydrochloric acid was added and stirred for 30 minutes. The contents were filtered through Nutsche, and the residue was washed with a small amount of methanol and then dried to obtain 42 g of pigment derivative VIII represented by the following formula (24).
Negative mode obtained with MALDI-TOF-MS mass spectrometer AXIMA CFR plus (manufactured by Shimadzu Corp.) using α-cyano-4-hydroxycyanic acid (CHCA) and 2,5-Dihydroxybenzoic acid (DHBA) as a matrix It was confirmed that there was a peak of the target product (m / z 407) in the spectrum.

Example 1
In a 100 mL container, 34.9 parts by weight of PMA, 6.74 parts by weight of pigment (manufactured by BASF, Chrophtal Orange K 2960, CI Pigment Orange 64), 0.75 parts by weight of derivative I, dispersant I 4.69 parts by weight (1.9 parts by weight of solid content), 141.3 parts by weight of zirconia beads having a diameter of 0.3 mm, and after stirring for 50 minutes with a paint shaker, 15.3 parts by weight of PMA was added for dilution. Then, the zirconia beads were removed to obtain an orange pigment dispersion.

(Examples 2 to 27, Comparative Examples 1 to 11)
A pigment dispersion was obtained in the same manner as in Example 1 except that the types and addition amounts of the pigment, pigment derivative and dispersant were changed as shown in Table 2.

The pigments and dispersants VII and VIII shown in Table 2 are as follows.
POr64: BASF "Chromophthal Orange K 2960"
PV23: “Hostaperm Violet RL-COF VP2717” manufactured by Clariant
PV29: "PERRINDO Violet 29" made by DIC
PB60: “Paliogen Blue L 6480” manufactured by BASF
PR179: "PERRINDO Maron 179 229-6438" manufactured by DIC
PBk7: “MCF88” manufactured by Mitsubishi Chemical Corporation
Lactam black: “Irgaphor Black S0100CF” manufactured by BASF PB15: 3: “Fastogen Blue 5380” manufactured by DIC
PB15: 6: “Fastogen Blue EP-207” manufactured by DIC
Dispersant VII: “DISPERBYK LPN21116” manufactured by Big Chemie (dispersant having quaternary ammonium and tertiary amine, acid value: 0 mgKOH / g, amine value: 75 mgKOH / g)
Dispersant VIII: “DISPERBYK-111” manufactured by Big Chemie (acid-type phosphate-based dispersant containing no amide group, acid value: 129 mgKOH / g, amine value: 0 mgKOH / g)

(Evaluation)
<Dispersion stability>
Immediately after preparing the pigment dispersions of Examples and Comparative Examples, the viscosity was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd. Further, after the pigment dispersion was stored at 25 ° C. for 1 week, the viscosity was measured in the same manner. The evaluation results are shown in Table 3. The pass / fail criterion is that the viscosity with time is within 200% (within 2 times) the initial viscosity.

<Developability>
In the pigment dispersions obtained in each example and comparative example, epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) 827) and acrylic resin (manufactured by Soken Chemical Co., Ltd., foret (registered) are used as coating film forming components. (Trademark) ZAH-310) (epoxy resin / acrylic resin = 3/1 (weight basis)) was added so that pigment / (resin + dispersant) = 1/2, and the non-volatile content was 25% by weight. PMA was added so that an evaluation sample was obtained. The pigment weight includes a pigment derivative.
Immediately after preparing this evaluation sample, a spin coater (Mikasa Co., Ltd., spin coater MS-150A) is used to form a film at 500 rpm on a 1 mm thick, 100 mm square non-alkali glass substrate and dried at room temperature for 3 minutes. Then, it dried at 90 degreeC on a hot plate for 2 minutes and 30 seconds, and the coating plate with which the coating film was formed on the glass substrate was obtained. This coated plate was developed using a 100-fold diluted solution of a developer “CD-150CR” manufactured by JSR at a wide-angle nozzle and a liquid temperature of 25 ° C., and developability (initial development time and state of development) was confirmed. Further, after the prepared evaluation sample was stored at 25 ° C. for 1 week, a coated plate was formed in the same manner as described above, and developability (development time with time and state of development) was confirmed. The evaluation results are shown in Table 3. In Table 3, the development time change rate is a percentage obtained by dividing the development time with the initial development time.

Further, the criteria of “dissolution” and “peeling” in Table 3 are as follows. It is determined that “dissolution” is practically usable and “peeling” is practically unusable.
Dissolution: It is clear visually that the coating film dissolves and flows during the developer shower.
Peeling: It is clear that the coating is peeled off during the developer shower.

(Production Example 15) Production of Dispersant IX Block copolymer IX was obtained in the same manner as in Production Example 1 except that N, N-dimethylacrylamide (DMAA) (manufactured by KJ Chemicals) was used instead of NIPAM. It was. The solid content of the reaction mixture was 40% by weight. When the obtained block copolymer IX was measured by GPC, the peak top molecular weight was 8800, and Mw / Mn was 1.19. The acid value was 0 mgKOH / g. The block copolymer IX is a linear second block in which a block IX-1 having a structural unit derived from MMA and a block IX-2 having a structural unit derived from BMA are connected to each other at one end. And a structural unit derived from DMAA linked to the other end of the block IX-2 (both R ^1a and R ^1b in formula (1) are —CH ₃ and R ² is a hydrogen atom). It has a first block with block IX-3. That is, the block copolymer IX is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer IX does not have a basic group. The weight ratio of each block of the block copolymer IX (block IX-1 / block IX-2 / block IX-3) is 33.7 / 32.7 / 33.6. Block copolymer IX was used as dispersant IX.

Production Example 16 Production of Dispersant X A block copolymer X was obtained in the same manner as in Production Example 1 except that 4-acryloylmorpholine (ACMO) (manufactured by KJ Chemicals) was used instead of NIPAM. The solid content of the reaction mixture was 40% by weight. When the obtained block copolymer X was measured by GPC, the peak top molecular weight was 8500, and Mw / Mn was 1.22. The acid value was 0 mgKOH / g. The block copolymer X is a linear second block in which a block X-1 having a structural unit derived from MMA and a block X-2 having a structural unit derived from BMA are connected to each other at one end. has, ^R 1a in the structural unit (formula (1) derived from ACMO linked to the other end of the block ^{X-2, R 1b} _is, -CH 2 -CH ₂ - to each other, are connected by -O- A first block having a block X-3 having a ring structure and R ² is a hydrogen atom. That is, the block copolymer X is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer X does not have a basic group. The weight ratio (block X-1 / block X-2 / block X-3) of each block of the block copolymer X is 33.7 / 32.7 / 33.6. Block copolymer X was used as dispersant X.

(Production Example 17) Production of Dispersant XI Block copolymer XI was obtained in the same manner as in Production Example 1 except that N, N-diethylacrylamide (DEAA) (manufactured by KJ Chemicals) was used instead of NIPAM. It was. The solid content of the reaction mixture was 40% by weight. When the obtained block copolymer XI was measured by GPC, the peak top molecular weight was 9500, and Mw / Mn was 1.19. The acid value was 0 mgKOH / g. The block copolymer XI is a linear second block in which a block XI-1 having a structural unit derived from MMA and a block XI-2 having a structural unit derived from BMA are connected to each other at one end. And a structural unit derived from DEAA linked to the other end of block XI-2 (R ^1a and R ^1b in formula (1) are both —CH ₂ CH ₃ and R ² is a hydrogen atom.) And a first block having a block XI-3. That is, the block copolymer XI is a linear block polymer having a first block at one end thereof. Due to the monomer structure, the block polymer X does not have a basic group. The weight ratio (block XI-1 / block XI-2 / block XI-3) of each block of the block copolymer XI is 33.7 / 32.7 / 33.6. Block copolymer XI was used as dispersant XI.

(Examples 28 to 33)
The pigments, pigment derivatives and dispersants were added in the same manner as in Example 1 except that the types and amounts added were as shown in Table 5 and the water concentration in the entire pigment dispersion was 1.0% by weight. A dispersion was obtained. The pigments shown in Table 5 mean the same pigments as in Table 2 except that PB60 (EH1900) is “Paliogen Blue EH1900” manufactured by BASF. Using the obtained pigment dispersion, dispersion stability and developability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 6.

As shown in Tables 3 and 6, the pigment dispersions of the examples and the evaluation samples using the pigment dispersions had good dispersion stability and developability, whereas the pigment dispersions of the comparative examples and the same were used. It can be seen that the evaluation sample is gelable and cannot be developed, or the dispersion stability is similar to that of the example, but the developability is inferior to the sample using the pigment dispersion of the example. Thus, by using a predetermined dispersant, the pigment dispersion has good dispersion stability. By using the pigment dispersion, for example, an epoxy resin containing an epoxy group is used as a coating film forming component. It can also be seen that good storage stability can be obtained. Moreover, the favorable solvent resistance at the time of setting it as a coating film can be anticipated by not containing a quaternary ammonium salt. Furthermore, as shown in Table 6, when a block copolymer containing an amide group that does not contain an N—H bond is included as a dispersant, good storage stability is obtained even when moisture is contained in the pigment dispersion. It can be seen that

Claims (8)

A pigment dispersion containing a pigment, a dispersant and a solvent (except for those containing a quaternary ammonium salt),
The dispersant has a linear structure having a first block having at least one selected from structural units represented by the following formulas (1), (2) and (2-2) at one end. A pigment dispersion which is a block polymer having a basic group and no basic group.

(In formula (1), R ^1a and R ^1b are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. And at least one is not a hydrogen atom, a hydrogen atom directly connected to a carbon atom contained in each hydrocarbon group of R ^1a and R ^1b is —C (═O) —NR ^5a R ^5b , —O -C (= O) -NR < ^6a > R < ^6b >, -NR < ⁷ > -C (= O) -NR < ^8a > R < ^8b >, a cyclic amide group, -OH or -COOH, and an aliphatic hydrocarbon group In the case where the number of carbon atoms is 2 to 12, at least one double bond may be included in the carbon-carbon bond, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( = O) -, - C ( = O) -O -, - O-C (= O) -, - C (= O) -NR 9 - ^{-NR 10 -C (= O) -} , - NR 11 -C (= O) -O -, - O-C (= O) -NR 12 - or ^{-NR 13 -C (= O) -NR} 14 - R ^{5a to} R ¹⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ^5a and R ^5b , R ^6a and R ^6b, and R 5 ^8a and ^{R 8b} are not each of the at least one of hydrogen atom, ^{R 7} and ^{R 8a} or ^{R 8b, R 13} and ^{R 14} are each, are connected by a divalent hydrocarbon group having 1 to 4 carbon atoms ring structures In R ^1a and R ^1b , the aliphatic hydrocarbon groups having 1 to 4 carbon atoms may be connected to each other by —O— to form a ring structure.
R ² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

(In formula (2), R ³ may have a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an N—H bond, including an amide group that may have an N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group is represented.
Aliphatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 15a} R 15b, -O-C (= O) -NR 16a R 16b, -NR ¹⁷ —C (═O) —NR ^18a R ^18b , a cyclic amide group, —OH or —COOH may be substituted, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( ═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ¹⁹ —, —NR ²⁰ —C (═O) —, —NR ²¹ -C (= O) -O -, - O-C (= O) -NR 22 - or ^{-NR 23 -C (= O) -NR} 24 - may be replaced. R ^{15a to} R ²⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ¹⁷ and R ^18a or R ^18b , R ²³ and R ²⁴ each have 1 to Nitrogen atoms may be connected by a divalent hydrocarbon group of 4 to form a ring structure. In addition, when the aliphatic hydrocarbon group has 2 to 12 carbon atoms, at least one double bond may be included in the carbon-carbon bond.
Aromatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 25a} R 25b, -O-C (= O) -NR 26a R 26b, -NR ²⁷ —C (═O) —NR ^28a R ^28b , a cyclic amide group, —OH or —COOH may be substituted. R ^{25a to} R ^28b each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ²⁷ and R ^28a or R ^28b represent a divalent carbon atom having 1 to 4 carbon atoms. Nitrogen atoms may be linked by a hydrogen group to form a ring structure.
R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. )

(In formula (2-2), R ²⁹ and R ⁴⁵ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Represents a hydrocarbon group and at least one is not a hydrogen atom.
Aliphatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 31a} R 31b, -O-C (= O) -NR 32a R 32b, -NR ³³ —C (═O) —NR ^34a R ^34b , a cyclic amide group, —OH or —COOH may be substituted, and —CH ₂ — constituting the aliphatic hydrocarbon group is —O—, —C ( ═O) —, —C (═O) —O—, —O—C (═O) —, —C (═O) —NR ³⁵ —, —NR ³⁶ —C (═O) —, —NR ^37. -C (= O) -O -, - O-C (= O) -NR 38 - or ^{-NR 39 -C (= O) -NR} 40 - may be replaced. R ^{31a to} R ⁴⁰ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ³³ and R ^34a or R ^34b , R ³⁹ and R ⁴⁰ , respectively, Nitrogen atoms may be connected by a divalent hydrocarbon group of 4 to form a ring structure. In addition, when the aliphatic hydrocarbon group has 2 to 12 carbon atoms, at least one double bond may be included in the carbon-carbon bond.
Aromatic hydrocarbon groups, hydrogen atoms directly bonded to the carbon atoms contained in the hydrocarbon ^{group, -C (= O) -NR 41a} R 41b, -O-C (= O) -NR 42a R 42b, -NR ⁴³ —C (═O) —NR ^44a R ^44b , a cyclic amide group, —OH or —COOH may be substituted. R ^{41a to} R ^44b each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and R ⁴³ and R ^44a or R ^44b are divalent carbon atoms having 1 to 4 carbon atoms. Nitrogen atoms may be linked by a hydrogen group to form a ring structure.
R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. ) In the structural unit represented by the formula (1), one of R ^1a and R ^{1b in} the formula (1) is a hydrogen atom,
The structural unit represented by the formula (2) is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an N— in which R ³ includes an amide group having an N—H bond in the formula (2). A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group having an H bond,
The structural unit represented by the formula (2-2) is a carbon that may include an amide group in which R ⁴⁵ is a hydrogen atom and R ²⁹ may have an N—H bond in the formula (2-2). A monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may include an amide group which may have an N-H bond, or R ²⁹ , At least one of R ⁴⁵ includes a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms including an amide group having an N—H bond or a monovalent group having 6 to 12 carbon atoms including an amide group having an N—H bond. The pigment dispersion according to claim 1, which is an aromatic hydrocarbon group of The structural unit represented by the formula (1) is a monovalent fat having 1 to 12 carbon atoms in which R ^1a and R ^{1b in the} formula (1) may include an amide group having no N—H bond. A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, which may include an aromatic hydrocarbon group or an amide group having no NH bond,
The structural unit represented by the formula (2) is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms including an amide group in which R ³ does not have an N—H bond in the formula (2) or A monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms including an amide group having no NH bond,
The structural unit represented by the formula (2-2) has 1 to 12 carbon atoms in which R ²⁹ and R ⁴⁵ may include an amide group having no N—H bond in the formula (2-2). The pigment dispersion according to claim 1, which is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may include a monovalent aliphatic hydrocarbon group or an amide group having no N-H bond.   The pigment dispersion according to any one of claims 1 to 3, wherein the block polymer includes a second block having a structural unit derived from a monomer having a polymerizable double bond.   The pigment dispersion according to claim 4, wherein the monomer having a polymerizable double bond is at least one selected from a nonionic water-soluble compound, an anionic water-soluble compound, and a nonionic water-insoluble compound.   Furthermore, the pigment dispersion in any one of Claims 1-5 containing the acidic pigment derivative which does not have a basic group.   The pigment dispersion according to any one of claims 1 to 6, which is used for a column spacer of a liquid crystal display device. The coloring composition containing the coating-film formation component containing the pigment dispersion and epoxy group in any one of Claims 1-7.