JP6605783B1 - Dispersant composition, coloring composition and color filter - Google Patents

Abstract

An object of the present invention is to provide a dispersant composition excellent in pigment dispersibility. A dispersant composition comprises (a) a block copolymer having an A block having an acidic group and a B block containing structural units represented by general formulas (1) and (2); (A) Aromatic compound; (c) A tertiary amine compound is mixed. [In the formulas (1) and (2), R11, R12, R13, R21 and R22 each independently represents a chain or cyclic hydrocarbon group which may have a substituent. . Two or more of R11, R12 and R13 may be bonded to each other to form a cyclic structure. R21 and R22 may be bonded to each other to form a cyclic structure. R14 and R23 each represents a hydrogen atom or a methyl group. X1 and X2 each represent a divalent linking group. Y- represents a counter ion. ] [Selection figure] None

Description

  The present invention relates to a dispersant composition, a colored composition containing the dispersant composition, and a color filter including a colored layer formed using the colored composition.

  Conventionally, in the production of a color filter used for a liquid crystal display or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, a printing method, and the like are known as methods for applying a coloring material to a substrate. Among these, the pigment dispersion method is widely used from the viewpoint of spectral characteristics, durability, pattern shape, and accuracy. In the pigment dispersion method, for example, a coating film made of a colored composition in which a pigment, a dispersant, a dispersion medium (solvent), etc. are mixed is formed on a substrate, exposed through a photomask having a desired pattern shape, and alkali development is performed. Is done.

  In recent years, color filters are required to have higher transmission, higher luminance, higher contrast, and higher color gamut. For this reason, various studies have been conducted, such as increasing the concentration of the pigment in the coloring composition and developing a pigment whose intrinsic transmission absorption spectrum matches the phosphor spectrum of the backlight.

  In particular, with respect to increasing the brightness of green pixels, new zinc halide phthalocyanine green pigments having a specific hue have been proposed as described in Patent Documents 1 and 2, for example. As a result, high brightness was achieved for the conventional copper halide phthalocyanine green pigment. Patent Document 3 includes a structural unit derived from a vinyl monomer having a tertiary amino group and a structural unit derived from a vinyl monomer having a quaternary ammonium base, and the content ratio of the quaternary ammonium base is 4 and It is disclosed to use a dispersant that is 60 mol% or less of the total content of the secondary ammonium base.

JP 2004-70342 A JP 2004-70343 A JP 2016-38584 A

  However, when the pigments described in Patent Documents 1 and 2 are used, the viscosity of the pigment dispersion increases, making it difficult to industrially produce a colored resin composition using the pigment dispersion. Further, the dispersant used in the method of Patent Document 3 is not sufficient in pigment dispersibility. The present invention has been made in view of the above circumstances, and an object thereof is to provide a dispersant composition excellent in pigment dispersibility.

  The dispersant composition of the present invention that has been able to solve the above-mentioned problems includes (a) an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a structural unit represented by the following general formula (1) And a block copolymer having a B block containing a structural unit represented by the following general formula (2), (b) an aromatic dicarboxylic imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound It is characterized in that it is formed by mixing at least one aromatic compound selected from the group consisting of: and (c) a tertiary amine compound.

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In Formula (1), R <^11> , R < ¹² > and R < ¹³ > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

〔式（２）において、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹およびＲ²²が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²³は水素原子またはメチル基を示す。〕

[In Formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

  When the dispersant composition of the present invention is used, a colored composition having a high dispersibility of the colorant and a low viscosity can be obtained. In particular, when a cyclic amidine compound is used as the (c) tertiary amine compound, the brightness of the coating film formed from the colored composition can also be improved.

  The dispersant composition of the present invention comprises (a) an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1) described later, and a general formula (2) described later. A block copolymer having a B block containing a structural unit represented by: (b) at least selected from the group consisting of aromatic dicarboxylic imides, acidic group-containing aromatic compounds and phenolic hydroxy group-containing aromatic compounds One type of aromatic compound; (c) a tertiary amine compound is mixed.

(A) Block copolymer The dispersant composition contains (a) a block copolymer. As the (a) block copolymer, only one type may be blended, or two or more types may be used in combination. The (a) block copolymer is represented by an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1) described later, and a general formula (2) described later. And a B block including the structural unit.

  In the present invention, “A block” can be rephrased as “A segment”, and “B block” can be rephrased as “B segment”. In the present invention, the “vinyl monomer” refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from a vinyl monomer” refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized into a carbon-carbon single bond. “(Meth) acryl” means “at least one of acrylic and methacrylic”. “(Meth) acrylate” means “at least one of acrylate and methacrylate”. “(Meth) acryloyl” refers to “at least one of acryloyl and methacryloyl”.

(Block A)
The A block is a polymer block having a structural unit derived from a vinyl monomer having an acidic group. It is thought that alkali development becomes easy because A block has an acidic group. Therefore, the block copolymer can be suitably used for a colored composition for a color filter used for producing a color filter employing alkali development.

Examples of the acidic group include a carboxy group (—COOH), a sulfonic acid group (—SO ₃ H), a phosphoric acid group (—OPO ₃ H ₂ ), a phosphonic acid group (—PO ₃ H ₂ ), and a phosphinic acid group (— PO ₂ H ₂ ). A block may have only 1 type of structural unit derived from the vinyl monomer which has an acidic group, and may have 2 or more types.

  The vinyl monomer having an acidic group is preferably at least one selected from a vinyl monomer having a carboxy group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphoric acid group. Among these, at least one selected from a (meth) acrylic monomer having a carboxy group, a (meth) acrylic monomer having a sulfonic acid group, or a (meth) acrylic monomer having a phosphoric acid group is preferable.

  Examples of the vinyl monomer having a carboxy group include (meth) acrylic acid; 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, hydroxy groups such as 2- (meth) acryloyloxyethyl phthalate A monomer obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride with a vinyl monomer (preferably hydroxyalkyl (meth) acrylate) having a carboxylic acid; crotonic acid; maleic acid; itaconic acid.

  Examples of the vinyl monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, ethyl disulfonate (meth) acrylate, methyl propyl sulfonic acid (meth) acrylamide, and ethyl sulfonate (meth) acrylamide.

  Examples of the vinyl monomer having a phosphoric acid group include 2- (phosphonooxy) ethyl (meth) acrylate.

  The content of the structural unit derived from the vinyl monomer having an acidic group is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and 20% by mass in 100% by mass of the A block. % Or less is preferable, more preferably 18% by mass or less, and still more preferably 16% by mass or less. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with an alkali is increased in alkali development, and if it is 20% by mass or less, the hydrophilicity is high. However, it is possible to prevent the formed pixels from becoming messy.

  The A block may have a structural unit other than the structural unit derived from the vinyl monomer having an acidic group. The other structural unit that can be contained in the A block is not particularly limited as long as it is formed by a vinyl monomer that can be copolymerized with both a vinyl monomer having an acidic group and a vinyl monomer that forms the B block described later. . Vinyl monomers that can form other structural units of the A block may be used alone or in combination of two or more.

  Specific examples of vinyl monomers that can form other structural units of the A block include α-olefins, aromatic vinyl monomers, vinyl monomers containing heterocycles, vinyl amides, vinyl carboxylates, dienes, and (meth) acrylic monomers. Etc. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of the α-olefin include 1-hexene, 1-octene, 1-decene and the like.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, 4-vinylpyridine and the like.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, 1-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and the like.
Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.

  (Meth) acrylic monomers include (meth) acrylates having a chain alkyl group (straight chain alkyl group or branched chain alkyl group); (meth) acrylates having a cyclic alkyl group (monocyclic structure); aromatic ring groups (Meth) acrylate having (meth) acrylamide; (meth) acrylate having a polyalkylene glycol structural unit; (meth) acrylate having a hydroxy group; (meth) acrylate having a lactone-modified hydroxy group; (meth) having an alkoxy group Acrylate; (meth) acrylate having a cyclic ether group and the like.

  Examples of the (meth) acrylate having a chain alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned. Examples of the (meth) acrylate having a cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. Examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.
Examples of the (meth) acrylate having a polyalkylene glycol structural unit include polyethylene glycol (polymerization degree = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree = 2 to 10) ethyl ether (meth) acrylate, polyethylene glycol (Degree of polymerization = 2 to 10) Propyl ether (meth) acrylate, polyethylene glycol (Degree of polymerization = 2 to 10) (Meth) acrylate having a polyethylene glycol structural unit such as phenyl ether (meth) acrylate; Polypropylene glycol (Degree of polymerization = 2-10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2-10) ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2-10) propyl ether (Meth) acrylate, polypropylene glycol (polymerization degree = 2-10) with polypropylene glycol structural units such as phenyl ether (meth) acrylate (meth) acrylate.

  As (meth) acrylate having a hydroxy group, hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. (Meth) acrylate etc. are mentioned.

  Examples of the (meth) acrylate having a lactone-modified hydroxy group include those obtained by adding a lactone to the (meth) acrylate having a hydroxy group, and those obtained by adding caprolactone are preferred. The amount of lactone added is preferably 1 mol to 10 mol, and more preferably 1 mol to 5 mol. Examples of the (meth) acrylate having a lactone-modified hydroxy group include 2-hydroxyethyl (meth) acrylate caprolactone 1 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 2 mol adduct, 2-hydroxyethyl (meth) acrylate. Caprolactone 3 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 5 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 10 mol adduct, and the like. It is done.

  Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.

  Examples of the (meth) acrylate having a cyclic ether group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, 2- (4-morpholinyl) ethyl (meth) acrylate, (3- Ethyl oxetane-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- [(2-Tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate and the like.

  The vinyl monomer that can form another structural unit that can be included in the A block is preferably a (meth) acrylic monomer, (meth) acrylate having a chain alkyl group, (meth) acrylate having an aromatic ring group, polyalkylene glycol It is at least one selected from the group consisting of (meth) acrylate having a structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, and (meth) acrylate having a cyclic ether group. It is more preferable. The vinyl monomer that can be used in the A block can be used alone or in combination of two or more.

  At least one vinyl monomer selected from the group consisting of (meth) acrylate having a chain alkyl group, (meth) acrylate having a cyclic alkyl group, and (meth) acrylate having an aromatic ring group In the case of having derived structural units, the total content of these structural units is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and still more preferably in 100% by mass of the A block. Is 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 98% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

  A block is (meth) acrylamide, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, (meth) acrylate having an alkoxy group, And when it has a structural unit derived from at least one vinyl monomer selected from the group consisting of (meth) acrylates having a cyclic ether group, the total content of these structural units is It is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, and still more preferably. Is less than 50% by weight, more preferably 3 Mass%, particularly preferably at most 20 mass%.

  Moreover, it is preferable that A block does not have an amino group. That is, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group. When a large amount of amino groups are present in the A block, the colorant is adsorbed by both the A block and the B block when used as a dispersant for the colorant, and the dispersibility of the colorant is deteriorated. The content of the structural unit derived from the vinyl monomer having an amino group in the A block is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and most preferably 0% by mass. %.

  When two or more types of structural units are contained in the A block, the various structural units contained in the A block may be contained in any form such as random copolymerization and block copolymerization in the A block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.

(B block)
The B block is a polymer block having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). Since the B block has a quaternary ammonium base in addition to the tertiary amino group, it is considered that the B block has a high affinity with the colorant.

(Structural unit represented by general formula (1))
The structural unit represented by the general formula (1) has a quaternary ammonium salt in the structure. The structural unit represented by the general formula (1) in the B block may be only one type or may have two or more types.

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In Formula (1), R <^11> , R < ¹² > and R < ¹³ > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

The chain hydrocarbon group represented by R ^{11 to} R ¹³ includes both straight and branched chains. Examples of the substituent of the chain hydrocarbon group represented by R ^{11 to} R ¹³ include a halogen group, an alkoxy group, a benzoyl group (—COC ₆ H ₅ ), and a hydroxy group. Examples of the substituent that the cyclic hydrocarbon group represented by R ^{11 to} R ¹³ has include a chain alkyl group, a halogen atom, an alkoxy group, and a hydroxy group.

Examples of the group represented by R ^{11 to} R ¹³ include an alkyl group having 1 to 4 carbon atoms which may have a substituent and an aralkyl group having 7 to 16 carbon atoms which may have a substituent. A methyl group, an ethyl group, a propyl group, and a benzyl group (—CH ₂ C ₆ H ₅ ) are more preferable.

Examples of the cyclic structure formed by bonding two or more of R ^{11 to} R ¹³ to each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these. . The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (1-1), (1-2), and (1-3).

〔一般式（１−１）、（１−２）、（１−３）において、Ｒ¹⁵は、Ｒ¹¹〜Ｒ¹³のいずれかである。Ｒ¹⁶は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ¹⁶は、それぞれ同一でも異なっていてもよい。〕

[In General Formulas (1-1), (1-2), and (1-3), R ¹⁵ is any one of R ^{11 to} R ¹³ . R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4. n represents an integer of 0 to 4. * Represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ¹⁶ may be the same or different. ]

In the general formula (1), examples of the divalent linking group X ¹ include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ¹⁷ — group (amide group), a —COO—R ¹⁸ — group. (ester group) and the like, preferably -CONH-R ¹⁷ - a group - groups and / or -COO-R ¹⁸ - a group, more preferably -COO-R ^18. The bonding direction of the amide group and the ester group is not particularly limited, but the bonding mode of the amide group is preferably C—CO—NH—R ¹⁷ —N ⁺ R ¹¹ R ¹² R ¹³ , and the bonding mode of the ester group is C—CO—O—R ¹⁸ —N ⁺ R ¹¹ R ¹² R ¹³ is preferred.

R ¹⁷ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

R ¹⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

Examples of Y ⁻ include a halogen anion, a carboxylate anion, a nitroxide anion, a sulfate anion, a sulfonate anion, and a phosphate anion.

Examples of the halogen anion include a fluoro anion, a chloro anion, a bromo anion, and an iodo anion.
Examples of the carboxylate anion include alkyl carboxylate anions such as acetate anion and propionate anion; and aromatic carboxylate anions such as benzoate anion.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkyl sulfonate anions such as methanesulfonate anion and ethanesulfonate anion; and aromatic sulfonate anions such as benzenesulfonate anion and toluenesulfonate anion.
Examples of the phosphate anion include alkyl phosphate anions such as methyl phosphate anion; aromatic phosphate anions such as phenyl phosphate anion.

  Specific examples of the vinyl monomer forming the structural unit represented by the formula (1) include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, and (meth) acryloyloxybutyltrimethylammonium chloride. , (Meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxy Propylbenzyldiethylammonium chloride, (meth) acryloyloxybutylbenzyldiethyl Ammonium chloride, (meth) acryloylamidopropylbenzyldimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethyl Benzyldimethylammonium bromide, (meth) acryloyloxypropylbenzyldimethylammonium bromide, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, Meta) Acrylo Illu Cibutylbenzyldiethylammonium bromide, (meth) acryloylamidopropylbenzyldimethylammonium bromide, (meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) acryloyloxybutyltrimethylammonium iodide (Meth) acryloyloxyethylbenzyldimethylammonium iodide, (meth) acryloyloxypropylbenzyldimethylammonium iodide, (meth) acryloyloxybutylbenzyldimethylammonium iodide, (meth) acryloyloxyethylbenzyldiethylammonium iodide, ( (Meth) acryloyloxypropylbenzyl diethylammonium iodide, (Meth) acryloyloxybutylbenzyldiethylammonium iodide, (meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxy Ethylbenzyldimethylammonium fluoride, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) acryloyloxybutylbenzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyl diethylammonium fluoride, (meth) acryloyloxypropylbenzyl Diethylammonium fluoride, (meth) acryloyloxybutylbenzyl diethyl Numonium fluoride, (meth) acryloyloxyethyltrimethylammonium = methyl sulfate, (meth) acryloyloxypropyltrimethylammonium = methylsulfate, (meth) acryloyloxybutyltrimethylammonium = methylsulfate, (meth) acryloyloxyethyldimethyl Ethylammonium = ethylsulfate, (meth) acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth) acryloyloxybutyldimethylethylammonium = ethylsulfate, (meth) acryloyloxyethyltrimethylammonium = toluene-4-sulfonate, (Meth) acryloyloxypropyltrimethylammonium = toluene-4-sulfonate, ( Data) acryloyloxybutyl trimethylammonium = toluene-4-sulfonate, (meth) acryloyl amidopropyl trimethylammonium = methyl sulfate, and (meth) acryloyl amidopropyl dimethylammonium = ethyl sulfate and the like.

  The content of the structural unit represented by the general formula (1) is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and 85% by mass in 100% by mass of the B block. % Or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less. By setting the content of the structural unit represented by the general formula (1) within this range, it is considered that the colorant has high affinity.

(Structural unit represented by general formula (2))
The structural unit represented by the general formula (2) has a tertiary amine structure. The structural unit represented by the general formula (2) in the B block may be only one type, or may have two or more types.

〔式（２）において、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹およびＲ²²が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²³は水素原子またはメチル基を示す。〕

[In Formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

The chain hydrocarbon group represented by R ²¹ or R ²² includes both linear and branched chains. Examples of the substituent that the chain hydrocarbon group represented by R ²¹ or R ²² has include a halogen group, an alkoxy group, a benzoyl group, and a hydroxy group. Examples of the substituent that the cyclic hydrocarbon group represented by R ²¹ or R ²² has include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxy group.

Examples of the group represented by R ²¹ or R ²² include an optionally substituted alkyl group having 1 to 4 carbon atoms and an optionally substituted aralkyl group having 7 to 16 carbon atoms. A methyl group, an ethyl group, a propyl group, and a benzyl group are more preferable.

Examples of the cyclic structure formed by combining R ²¹ or R ²² with each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (2-1), (2-2), and (2-3).

〔一般式（２−１）、（２−２）、（２−３）において、Ｒ²⁴は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ²⁴は、それぞれ同一でも異なっていてもよい。〕

[In General Formulas (2-1), (2-2), and (2-3), R ²⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4. n represents an integer of 0 to 4. * Represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ²⁴ may be the same or different. ]

In the general formula (2), examples of the divalent linking group X ² include an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ²⁵ — group (amide group), —COO—R ²⁶ —. A group (ester group) and the like, preferably —COO—R ²⁶ — group and / or —CONH—R ²⁵ — group, preferably —CONH—R ²⁵ — group and / or —COO—R ²⁶ —. Group, more preferably a —COO—R ²⁶ — group. The bonding direction of the amide group and the ester group is not particularly limited, but the bonding mode of the amide group is preferably C—CO—NH—R ²⁵ —NR ²¹ R ²² , and the bonding mode of the ester group is C—CO —O—R ²⁶ —NR ²¹ R ²² is preferred.

R ²⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

R ²⁶ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably. Is an alkylene group having 1 to 4 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

  The content of the structural unit represented by the general formula (2) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and further preferably 30% in 100% by mass of the B block. More preferably, it is 40 mass% or more, 70 mass% or less is preferable, More preferably, it is 65 mass% or less, More preferably, it is 60 mass% or less. By setting the content of the structural unit represented by the general formula (2) within this range, it is considered that the colorant has high affinity.

  The B block may be only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may include other structural units. From the viewpoint of maintaining affinity with the colorant, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is 80% by mass or more. Is preferable, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Moreover, it is preferable that B block does not contain the structural unit derived from the vinyl monomer which has an acidic group substantially. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, and more preferably 3% by mass or less in 100% by mass of the B block.

  Specific examples of the vinyl monomer capable of forming another structural unit of the B block include the same ones as exemplified as specific examples of the vinyl monomer capable of forming the other structural unit of the A block.

  When two or more types of structural units are contained in the B block, the various structural units contained in the B block may be contained in any form such as random copolymerization and block copolymerization in the B block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization. For example, the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B. when expressed as, _{(a-B) m} type, _(a-B) m -A type, the group consisting of _(B-a) m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) It is preferably a copolymer having at least one structure selected from Among these, a diblock copolymer represented by AB is preferable from the viewpoint of handleability during processing and physical properties of the composition. By constituting the diblock copolymer represented by AB, it is derived from a structural unit derived from a vinyl monomer having an acidic group in the A block and a vinyl monomer having a tertiary amino group in the B block. It is considered that the structural unit and the structural unit derived from the vinyl monomer having a quaternary ammonium base are localized, and can efficiently act suitably with the colorant, the solvent, and the binder resin (alkali-soluble resin).

  The content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and still more preferably 50% by mass or more in 100% by mass of the entire block copolymer. 85 mass% or less, more preferably 80 mass% or less, still more preferably 75 mass% or less, and still more preferably 65 mass% or less. The content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and still more preferably 30% by mass or more in 100% by mass of the entire block copolymer. 65 mass% or less, more preferably 60 mass% or less, still more preferably 55 mass% or less, still more preferably 50 mass% or less, and even more preferably 45 mass% or less. By adjusting the content ratios of the A block and the B block within the above ranges, the heat resistance and the dispersion performance when used as a dispersant can be balanced.

  The mass ratio of the A block to the B block in the block copolymer (A block / B block) is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, and 95 / 5 or less, more preferably 90/10 or less, still more preferably 80/20 or less, and still more preferably 70/30 or less. When the mass ratio between the A block and the B block is within the above range, the dispersion performance and alkali developability when used as a dispersant can be balanced.

  The content of the structural unit derived from the vinyl monomer having an acidic group in the block copolymer (a) is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 4% by mass or more. 20 mass% or less is preferable, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

  The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer (a) is preferably 5% by mass or more, more preferably. It is 10 mass% or more, More preferably, it is 20 mass% or more, 50 mass% or less is preferable, More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less.

  The molecular weight of the (a) block copolymer is measured by gel permeation chromatography (hereinafter referred to as “GPC”) method. The weight average molecular weight (Mw) of the block copolymer (a) is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, and still more preferably 10,000. It is as follows. When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

  The molecular weight distribution (PDI) of the (a) block copolymer is preferably 2.0 or less, more preferably 1.6 or less, and even more preferably 1.4 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer) / (number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the molecular weight distribution and the more uniform the copolymer. When the value is 1.0, the molecular weight distribution is the narrowest. That is, the lower limit value of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, one having a low molecular weight or one having a high molecular weight is included.

(Method for producing block copolymer)
The block copolymer is produced by a method in which an A block is first produced by a polymerization reaction of a vinyl monomer, and a B block monomer is polymerized in the A block; A method of polymerizing block monomers; A block and B block are produced separately, and then A block and B block are coupled; A block is produced first, and B block is represented by formula (2). A monomer composition containing a vinyl monomer capable of forming a structural unit is polymerized, and a part of the tertiary amine structure of the structural unit represented by the formula (2) in the obtained polymer is quaternized. Method: A monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (2) is polymerized, and a monomer of an A block is polymerized to the polymer, and the formula ( ) A method of quaternizing a part of the tertiary amine structure of the structural unit represented by: A block and a block having the structural unit represented by the formula (2) are produced separately, and these blocks are cupped Examples include a method of quaternizing a tertiary amine structure of a part of the structural unit represented by the formula (2) in the obtained polymer after ringing.

  The polymerization method is not particularly limited, but living radical polymerization is preferred. In other words, the block copolymer is preferably polymerized by living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the termination of the growth end occurs due to the termination reaction and the chain transfer reaction, and the polymer tends to be a mixture of polymers having various molecular weights and heterogeneous compositions. In contrast, the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, but it is difficult to cause a termination reaction or chain transfer, and the growth end grows without being deactivated. Precise control is preferable in that the production of a polymer having a uniform composition is easy.

  In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); There are methods such as a method to be used (TERP method). Since the ATRP method uses an amine-based complex, it may not be used without protecting the acidic group of the vinyl monomer having an acidic group. In the RAFT method, when various monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be a problem such as sulfur odor or coloring. Among these methods, the TERP method is preferably used from the viewpoint of diversity of usable monomers, molecular weight control in the polymer region, uniform composition, or coloring.

  The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator. For example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and WO 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) A vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (11).
(B) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (11) and an azo polymerization initiator.
(C) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (11) and an organic ditelluride compound represented by the general formula (12).
(D) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (11), an azo polymerization initiator, and an organic ditelluride compound represented by the general formula (12).

［一般式（１１）において、Ｒ¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を示す。Ｒ²およびＲ³は、それぞれ独立に、水素原子または炭素数１〜８のアルキル基を示す。Ｒ⁴は、炭素数１〜８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を示す。
一般式（１２）において、Ｒ¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を示す。］

[In General formula (11), R < ¹ > shows a C1-C8 alkyl group, an aryl group, or an aromatic heterocyclic group. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group, or a propargyl group.
In the general formula (12), R ¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.

The groups represented by R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ⁴ is a C 1-8 alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or A propargyl group, specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl. And a linear or branched alkyl group such as an octyl group, a cyclic alkyl group such as a cyclohexyl group, and the like. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. A phenyl group is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent. Examples of the substituent of the aryl group having the substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR ⁴¹¹ (R ⁴¹¹ is carbon. (C1-C8 alkyl group, aryl group, C1-C8 alkoxy group or aryloxy group), sulfonyl group, trifluoromethyl group and the like. These substituents are preferably substituted by 1 or 2 substituents.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
As the alkoxy group, a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom is preferable. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert- Examples include butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include —CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
As the oxycarbonyl group, a group represented by —COOR ⁴³¹ (R ⁴³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable, and examples thereof include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group. Group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.
As the allyl group, —CR ⁴⁴¹ R ⁴⁴² —CR ⁴⁴³ ═CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ are And each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be linked by a cyclic structure).
As the propargyl group, —CR ⁴⁵¹ R ⁴⁵² —C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁵³ is a hydrogen atom and an alkyl group having 1 to 8 carbon atoms) , Aryl group or silyl group).

  Specific examples of the organic tellurium compound represented by the general formula (11) include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2- Methyl-2-n-butylterranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylterranyl-propionate or (3-trimethylsilylpropargyl ) -2-methyl-2-methylterranyl-propionate, etc., organics described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870 All of tellurium compounds It can be exemplified.

  Specific examples of the organic ditelluride compound represented by the general formula (12) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di -N-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis Examples include-(p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride.

  The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) ) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid ) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4) -Dimethylvaleronitrile) (V-70), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) Lopan], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Examples include azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), and the like.

  The polymerization step is a container substituted with an inert gas. For the purpose of promoting reaction, controlling molecular weight and molecular weight distribution, etc., depending on the type of vinyl monomer, the vinyl monomer and the organic tellurium compound of the general formula (11). An azo polymerization initiator and / or an organic ditelluride compound of the general formula (12) is mixed. At this time, examples of the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferable.

  What is necessary is just to adjust suitably the usage-amount of the vinyl monomer in said (a), (b), (c) and (d) according to the physical property of the target copolymer. The vinyl monomer is preferably 5 mol to 10000 mol with respect to 1 mol of the organic tellurium compound of the general formula (11).

  When the organic tellurium compound of the general formula (11) of (b) and the azo polymerization initiator are used in combination, the azo polymerization initiator is added in an amount of 0.01 mol to 10 mol with respect to 1 mol of the organic tellurium compound of the general formula (11). It is preferable that

  When the organic tellurium compound of the general formula (11) of the above (c) and the organic ditelluride compound of the general formula (12) are used in combination, the organic of the general formula (12) is used with respect to 1 mol of the organic tellurium compound of the general formula (11). The ditelluride compound is preferably 0.01 mol to 100 mol.

  When the organic tellurium compound of the general formula (11) of (d), the organic ditelluride compound of the general formula (12), and the azo polymerization initiator are used in combination, it is generally used for 1 mol of the organic tellurium compound of the general formula (11). The organic ditelluride compound of the formula (12) is preferably 0.01 mol to 100 mol, and the azo polymerization initiator is preferably 0.01 mol to 100 mol with respect to 1 mol of the organic tellurium compound of the general formula (11).

  The polymerization reaction can be carried out without a solvent, but it may be carried out using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture. Examples of aprotic solvents that can be used include anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform. , Carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene, and the like. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.

  The amount of the solvent used may be adjusted as appropriate. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less with respect to 1 g of vinyl monomer. More preferably, it is 10 ml or less, More preferably, it is 1 ml or less.

  The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but are usually stirred at 0 ° C. to 150 ° C. for 1 minute to 100 hours. The TERP method can obtain a high yield and a precise molecular weight distribution even at a low polymerization temperature and a short polymerization time. At this time, the pressure is usually normal pressure, but it may be increased or decreased.

  After the completion of the polymerization reaction, the intended copolymer can be separated from the obtained reaction mixture by removing the solvent used, residual vinyl monomer, and the like by a normal separation and purification means.

  The block copolymer of the present invention can be obtained, for example, by sequentially polymerizing vinyl monomers constituting the block by a living radical polymerization method. Specifically, in the case of an AB block, a step of polymerizing a vinyl monomer constituting the A block by a living radical polymerization method to polymerize the A block, and a vinyl monomer constituting the B block after polymerizing the A block In the case of the ABA block, the vinyl monomer constituting one of the two A blocks is polymerized by the living radical polymerization method, After polymerizing the A block, after polymerizing one A block, polymerizing the vinyl monomer constituting the B block, polymerizing the B block, and after polymerizing the B block, A polymerization method including a step of polymerizing a vinyl monomer constituting the other block and polymerizing the other A block.

The growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ¹ derived from a tellurium compound (wherein R ¹ is the same as described above), and is deactivated by operation in air after the completion of the polymerization reaction. However, tellurium atoms may remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or inferior in thermal stability, it is preferable to remove the tellurium atom.

  As a method for removing the tellurium atom, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbent, etc .; ion exchange resin; etc. Adsorption of metals with hydrogen peroxide: Add peroxide such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose the tellurium atom at the end of the copolymer, washing with water or appropriate A liquid-liquid extraction method or a solid-liquid extraction method that removes residual tellurium compounds by combining various solvents; a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. These methods can also be used in combination.

  When the tertiary amine group of the structural unit represented by the formula (2) is quaternized, the quaternizing agent includes alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; benzyl chloride Aralkyl halides such as benzyl bromide and benzyl iodide; diaryl sulfates such as diphenyl sulfate; dimethyl sulfate; dialkyl sulfates such as diethyl sulfate and di-n-propyl sulfate; methyl p-toluenesulfonate; p-toluenesulfonic acid Examples thereof include an alkyl alkyl sulfonate such as ethyl. Among these, preferably aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate, methyl p-toluenesulfonate, p-toluenesulfone Aromatic alkyl sulfonates such as ethyl acid, and more preferably benzyl chloride, dimethyl sulfate, and methyl p-toluenesulfonate. In the structure after quaternization, an alkyl group and an aralkyl group derived from a quaternizing agent are introduced. Therefore, the amount of the structural unit represented by the formula (1) can be estimated by measuring the amount of the alkyl group and aralkyl group introduced by quaternization.

  Examples of a method for quaternizing a tertiary amine structure of a part of the structural unit represented by the formula (2) in the polymer include a method of bringing the polymer and a quaternizing agent into contact with each other. Specifically, after polymerizing a monomer composition containing a vinyl monomer capable of forming the structural unit represented by the formula (2), a quaternizing agent is added to the reaction solution and stirred. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 25 ° C to 65 ° C, more preferably 55 ° C to 65 ° C, and the stirring time is preferably 1 hour to 40 hours, more preferably 5 hours to 20 hours. It is. When adding the quaternizing agent, it is also preferable to dilute the reaction solution after polymerization. Examples of the solvent added for dilution include a solvent that can be used for the polymerization reaction, a protic solvent, and a mixed solvent of the solvent used for the polymerization reaction and the protic solvent, depending on the solubility of the target block copolymer. What is necessary is just to select suitably. As the protic solvent, methanol is more preferable.

(B) Aromatic Compound The dispersant composition of the present invention is at least one selected from the group consisting of (b) an aromatic dicarboxylic imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound. Contains aromatic compounds. Dispersibility becomes favorable because a dispersing agent composition contains the aromatic compound (b). (B) An aromatic compound may mix | blend only 1 type and may use 2 or more types together.

  The aromatic dicarboxylic acid imide has an aromatic ring and an imide group (—C (═O) NHC (═O) —) directly bonded to the aromatic ring in the molecule. Both ends of the imide group may be bonded to one aromatic ring or may be bonded to different aromatic rings, but it is preferable that both ends are bonded to one aromatic ring. As said aromatic dicarboxylic imide, the compound represented by General formula (3) is preferable.

〔一般式（３）において、環Ａは置換基を有していてもよい芳香環を表す。〕

[In General Formula (3), Ring A represents an aromatic ring which may have a substituent. ]

  In the general formula (3), the aromatic ring constituting the ring A is a ring structure having aromaticity. The aromatic ring includes both single rings and condensed rings. As the monocycle, a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable. As the condensed ring, a 2 to 5 condensed ring is preferable, and a naphthalene ring, an anthracene ring, a phenanthrene ring, and an indole ring are preferable. Among these, the ring structure is preferably one that does not contain a hetero atom as an atom constituting the ring structure. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

  Specific examples of the aromatic dicarboxylic imide include the following compounds.

The acidic group-containing aromatic compound has an aromatic ring and an acidic group directly bonded to the aromatic ring in the molecule. Examples of the acidic group include a carboxy group (—COOH), a sulfonic acid group (—SO ₃ H), a phosphoric acid group (—OPO ₃ H ₂ ), a phosphonic acid group (—PO ₃ H ₂ ), and a phosphinic acid group (— PO ₂ H ₂ ). The number of acidic groups may be one or plural. Moreover, when it has multiple acidic groups, you may have multiple types of acidic groups. As the acidic group-containing aromatic compound, a compound represented by the general formula (4) (that is, aromatic carboxylic acid, aromatic sulfonic acid, aromatic phosphonic acid) is preferable.

〔一般式（４）において、環Ａは置換基を有していてもよい芳香環を表す。〕

[In General formula (4), the ring A represents the aromatic ring which may have a substituent. ]

  In the general formula (4), the aromatic ring constituting the ring A is a ring structure having aromaticity. The aromatic ring includes both single rings and condensed rings. As the monocycle, a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable. As the condensed ring, a 2 to 5 condensed ring is preferable, and a naphthalene ring, an anthracene ring, a phenanthrene ring, and an indole ring are preferable. Among these, the ring structure is preferably one that does not contain a hetero atom as an atom constituting the ring structure. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

  Specific examples of the aromatic carboxylic acid include the following compounds.

  Specific examples of the aromatic sulfonic acid include the following compounds.

  Specific examples of the aromatic phosphonic acid include the following compounds.

  The phenolic hydroxy group-containing aromatic compound has an aromatic ring and a hydroxy group directly bonded to the aromatic ring in the molecule. The number of hydroxy groups may be one or plural. As said phenolic hydroxy group containing aromatic compound, the compound represented by General formula (5) is preferable.

〔一般式（５）において、環Ａは置換基を有していてもよい芳香環を表す。〕

[In General Formula (5), Ring A represents an aromatic ring which may have a substituent. ]

  In the general formula (5), the aromatic ring constituting the ring A is a ring structure having aromaticity. The aromatic ring includes both single rings and condensed rings. As the monocycle, a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable. As the condensed ring, a 2-5 condensed ring is preferable, and a naphthalene ring, an anthracene ring, a phenanthrene ring, an indole ring, a coumarin ring, and a xanthene ring are preferable. Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.

  Specific examples of the phenolic hydroxy group-containing aromatic compound include the following compounds.

(C) Tertiary amine compound The dispersant composition contains (c) a tertiary amine compound. The (c) tertiary amine compound has a tertiary amine structure in the molecule. When the dispersant composition contains (c) a tertiary amine compound, salt formation with the (b) aromatic compound becomes possible. (C) Only one type of tertiary amine compound may be blended, or two or more types may be used in combination.

  As said (c) tertiary amine compound, the compound represented by General formula (6) or the compound represented by General formula (7) is preferable, and the compound represented by General formula (7) is more preferable. By blending the compound represented by the general formula (7) as the (c) tertiary amine compound, the brightness of the coating film formed from the colored composition is improved.

〔一般式（６）において、Ｒ⁶¹、Ｒ⁶²およびＲ⁶³は、それぞれ独立して、置換基を有してもよい炭素数１〜１０の炭化水素基を示す。また、Ｒ⁶²およびＲ⁶³は互いに結合して環状構造を形成してよい。〕

[In General Formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁶² and R ⁶³ may combine with each other to form a cyclic structure. ]

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶¹ , R ⁶² and R ⁶³ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and 6 to 10 carbon atoms. Aryl groups having 7 to 10 carbon atoms, and alkylaryl groups having 7 to 10 carbon atoms.

  Examples of the compound represented by the general formula (6) include aliphatics such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, and N-ethyldiamilamine. Examples include amines; aromatic amines such as N, N-dimethylaniline and N, N-diethylaniline; and alicyclic amines such as N, N-dimethyl-cyclohexylamine and N, N-diethyl-cyclohexylamine.

〔一般式（７）において、Ｒ⁷¹は置換基を有してもよい炭素数２〜６の２価の炭化水素基を示し、Ｒ⁷²およびＲ⁷³は、それぞれ独立して、水素原子または置換基を有してもよい炭素数１〜１０の炭化水素基を示す。また、Ｒ⁷²およびＲ⁷³は互いに結合して環状構造を形成してよい。〕

[In the general formula (7), R ⁷¹ represents an optionally substituted divalent hydrocarbon group having 2 to 6 carbon atoms, and R ⁷² and R ⁷³ each independently represents a hydrogen atom or a substituent. The C1-C10 hydrocarbon group which may have a group is shown. R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure. ]

Examples of the divalent hydrocarbon group having 2 to 6 carbon atoms represented by R ^71, include an alkylene group having 2 to 6 carbon atoms. Examples of the substituent of the divalent hydrocarbon group having 2 to 6 carbon atoms represented by R ⁷¹ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. -10 aryl group, C7-10 aralkyl group, C7-10 alkylaryl group.

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁷² and R ⁷³ include a chain alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. , An aralkyl group having 7 to 10 carbon atoms, and an alkylaryl group having 7 to 10 carbon atoms.

  As the compound represented by the general formula (7), a cyclic amidine compound represented by the general formula (8) is preferable.

〔一般式（８）において、Ｒ⁸⁰〜Ｒ⁸⁹は、それぞれ独立して、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基を示す。ｎは、１〜４の整数である。ｍは１〜４の整数である。〕

In [Formula (8), R ⁸⁰ ~R ⁸⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms. n is an integer of 1 to 4. m is an integer of 1-4. ]

  Specific examples of the compound represented by the general formula (8) include the following compounds.

  The dispersant composition preferably contains a solvent. As the solvent, an organic solvent can be used. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3 -Methyl-3-methoxybutanol, Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, Glycol dialkyl ethers such as dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether Glycol alkyl ether acetates such as acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; ethylene glycol diacetate, 1,3- Spotted Glycol diacetates such as lenglycol diacetate and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, Ethers such as ethyl isobutyl ether and dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone , Ketones such as methylnonyl ketone and methoxymethylpentanone; ethanol, propanol, Mono- or polyhydric alcohols such as diol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol; n- Aliphatic hydrocarbons such as pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; benzene, toluene , Xylene, cumene and other aromatic hydrocarbons; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutylene , Ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Linear or cyclic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone; 3-methoxypropionic acid, 3-ethoxypropion Alkoxycarboxylic acids such as acids; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrileThe organic solvent contained in the dispersant composition may be only one type or a plurality of types.

  The dispersant composition can be prepared by mixing (a) a block copolymer, (b) an aromatic compound, (c) a tertiary amine compound and, if necessary, a solvent. In addition, since it is thought that (b) aromatic compound and (c) tertiary amine compound react and form an organic salt after mixing, (b) aromatic compound and (c) tertiary amine are considered in advance. You may adjust by mixing the mixture (For example, (d) salt which consists of an aromatic compound and a tertiary amine compound) mixed with the compound, and (a) block copolymer. Each raw material can be mixed using, for example, a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader. The mixing temperature when preparing the dispersant composition is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, further preferably 60 ° C. or higher, 75 ° C. or lower, more preferably 70 ° C. or lower, and still more preferably. Is 65 ° C. or lower.

  The dispersant composition has a molar ratio of the quaternary ammonium base in the block copolymer (a) to the aromatic compound (b) (the quaternary ammonium base in (b) / (a)). 0.5 or more is preferable, More preferably, it is 0.8 or more, More preferably, it is 1.0 or more, 1.2 or less is preferable, More preferably, it is 1.1 or less, More preferably, it is 1.05 or less.

  The dispersant composition has a molar ratio of (a) quaternary ammonium base in the block copolymer to (c) tertiary amine compound ((c) / quaternary ammonium base in (a)). 0.5 or more, more preferably 0.8 or more, further preferably 1.0 or more, 1.2 or less, more preferably 1.1 or less, still more preferably 1.05 or less. .

  The dispersant composition comprises (a) a molar ratio ((c) / ((a) of the total of the acidic group in the block copolymer and the aromatic compound (b) and the tertiary amine compound (c). ) Is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably 1.0 or less, more preferably 0.9. Below, it is 0.8 or less more preferably.

  In the dispersant composition, the molar ratio ((b) / (c)) between the aromatic compound (b) and the tertiary amine compound ((b) / (c)) is preferably 0.9 or more, more preferably 0.8. It is 95 or more, More preferably, it is 1.0 or more, 1.1 or less is preferable, More preferably, it is 1.05 or less, More preferably, it is 1.02 or less.

  The amount of the solvent used is preferably 50 parts by mass or more, more preferably 100 parts by mass when the total of the (a) block copolymer, (b) aromatic compound and (c) tertiary amine compound is 100 parts by mass. 100 parts by mass or more, more preferably 200 parts by mass or more, preferably 500 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 250 parts by mass or less.

  The acid value of the solid content of the dispersant composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, preferably 70 mgKOH / g or less, more preferably 65 mgKOH / g. g or less, more preferably 60 mgKOH / g or less. If the acid value is 5 mgKOH / g or more, the solubility in alkali is high, and the rate of dissolution in alkali is faster. If the acid value is 70 mgKOH / g or less, the viscosity of the coloring composition does not become too high. The coatability becomes better. Here, the solid content is a component other than the solvent.

  The amine value of the solid content of the dispersant composition is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, still more preferably 50 mgKOH / g or more, preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g. g or less, more preferably 95 mgKOH / g or less. If the amine value is 10 mgKOH / g or more, the temporal stability of the viscosity of the colored composition is further improved, and if it is 150 mgKOH / g or less, an increase in the viscosity of the colored composition can be suppressed.

(Coloring composition)
The coloring composition of this invention contains the said dispersing agent composition, a coloring material, a dispersion medium, and binder resin.

(Coloring material)
What is necessary is just to select the kind of said coloring material suitably according to the use, for example, a pigment and dye are mentioned. The colored composition preferably contains a pigment as a coloring material from the viewpoint of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment mainly composed of an organic compound is particularly preferable. Examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment. The structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo Examples thereof include polycyclic pigments such as pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. Only one type of pigment may be included in the coloring composition, or a plurality of types may be used for adjusting chromaticity and the like.

  Specific examples of the pigment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 166, 168, Red pigments such as 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 242, 254, 255, 264, 269; I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213; I. Orange pigments such as CI Pigment Orange 36, 38, 43; I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 22, 60, and the like; C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxy Green pigments such as phosphinyloxyaluminum phthalocyanine and polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; I. And purple pigments such as Pigment Violet 23, 32, and 50. Among these pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 269, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and the like are preferable.

  In the present invention, the dispersant composition is preferably used together with a colorant containing a phthalocyanine pigment, and specifically, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 17, Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59, C.I. I. Pigment Green 62, C.I. I. Pigment Green 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxyphosphinyloxyaluminum phthalocyanine, polyhalogenated It is preferably used together with a coloring material containing diphenylphosphinyloxyaluminum phthalocyanine and the like. More preferably, it is used with a colorant containing a polyhalogenated phthalocyanine pigment.

  When forming a light shielding material such as a black matrix of a color filter by using the colored composition of the present invention, a black pigment can be used. The black pigment may be used alone, or may be used by mixing the red pigment, the green pigment, the blue pigment and the like. Examples of black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.

  The number average particle diameter of the colorant may be appropriately selected according to the application and is not particularly limited. The colored composition preferably contains a colorant having a number average particle diameter of 10 nm to 150 nm from the viewpoint of high transparency and high contrast.

  The colorant may contain a pigment derivative as a dispersion aid. The dye derivative preferably contains an acidic dye derivative having an acidic group so as to be ion-bonded and adsorbed with a tertiary amino group or a quaternary ammonium base in the resin-type dispersant. This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, a skeleton that is the same as or similar to the coloring material constituting the coloring composition, and a skeleton that is the same as or similar to the compound that is a raw material of the coloring material are preferable. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton. The acidic group introduced into the dye skeleton is preferably a carboxy group, a phosphoric acid group, or a sulfonic acid group. In addition, a sulfonic acid group is preferable from the viewpoint of synthesis and the strength of acidity. The acidic group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond. Although the usage-amount of a pigment derivative does not have limitation in particular, For example, it is preferable that they are 4 mass parts-17 mass parts with respect to 100 mass parts of coloring materials.

  The upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 75% by mass, and preferably 70% by mass in the total solid content of the coloring composition from the viewpoint of luminance. It is more preferable. Further, the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 30% by mass, more preferably 50% by mass in the total solid content of the coloring composition. preferable. Here, solid content is components other than the dispersion medium mentioned later.

  The content of the block copolymer (a) with respect to the coloring material in the coloring composition is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the coloring material, and is 10 parts by mass to 100 parts by mass. Is preferable, and it is more preferable that it is 10 mass parts-80 mass parts.

(Dispersion medium)
The coloring composition is appropriately selected as a dispersion medium as long as it disperses or dissolves other components constituting the coloring composition and does not react with these components and has moderate volatility. Can be used. For example, conventionally known organic solvents can be used, and those exemplified as the solvent for the dispersant composition can be used. The organic solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of the coloring material, solubility of the dispersant, applicability of the coloring composition, and the like. The solvent contained in the coloring composition may be only one type or a plurality of types.

  When forming a pixel of a color filter by a photolithography method, the boiling point of the dispersion medium is preferably 100 ° C. to 200 ° C. (under a pressure of 101.25 hPa. The same applies to the boiling points hereinafter), and 120 ° C. to 170 ° C. is preferable. More preferred. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferable from the viewpoints of good balance of coatability, surface tension, and the like, and relatively high solubility of the constituent components in the colored composition. Glycol alkyl ether acetates may be used alone or in combination with other dispersion media. In this case, it is also preferable to use a dispersion medium having a boiling point of 150 ° C. or higher. By using such a dispersion medium having a high boiling point, the colored composition becomes difficult to dry, and the destruction of the mutual relationship of the colored composition due to rapid drying can be suppressed. The content of the dispersion medium having a boiling point of 150 ° C. or higher is preferably 3% by mass to 50% by mass with respect to 100% by mass of the entire dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress the occurrence of foreign matter defects due to precipitation and solidification of the coloring material at the tip of the slit nozzle. If it is 50 mass% or less, the drying rate of a coloring composition will become slow, and generation | occurrence | production of problems, such as prolonged drying time and the pin mark of a prebaking in color filter manufacture mentioned later can be suppressed. The dispersion medium having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates. In this case, a dispersion medium having a boiling point of 150 ° C. or higher may not be included separately.

  When forming a pixel of a color filter by the inkjet method, the boiling point of the dispersion medium is preferably 130 ° C to 300 ° C, and more preferably 150 ° C to 280 ° C. By setting the boiling point to 130 ° C. or higher, the uniformity of the obtained coating film is improved. Moreover, the residual solvent in the coating film after heat baking can be reduced by making a boiling point into 300 degrees C or less, and the malfunction on quality and the prolongation of drying time can be suppressed. Further, the vapor pressure of the dispersion medium is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several pL to several tens of pL, so the dispersion medium evaporates before landing on the periphery of the nozzle opening or in the pixel bank. Tends to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the dispersion medium is high. Specifically, it is preferable to include a dispersion medium having a boiling point of 180 ° C. or higher. More preferably, it contains a dispersion medium having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Further, the high boiling point solvent having a boiling point of 180 ° C. or more is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass with respect to 100% by mass of the entire dispersion medium contained in the coloring composition. The above is most preferable. There exists a tendency which can fully exhibit the evaporation prevention effect of the solvent from a droplet by setting it as the said lower limit or more.

  Content of the dispersion medium in a coloring composition is not specifically limited, It can adjust suitably. The upper limit of the content of the dispersion medium in the coloring composition is usually 99% by mass. Further, the lower limit of the content of the dispersion medium in the colored composition is usually 70% by mass and preferably 75% by mass in consideration of the viscosity suitable for application of the colored composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the coloring composition.

(Binder resin)
The colored composition of the present invention contains a binder resin (however, the above (a) block copolymer is excluded). Thereby, the alkali developability of a coloring composition and the binding property to a board | substrate can be improved. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group. As the binder resin, for example, with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer is unsaturated monobasic. Resin obtained by adding an acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxy group generated by the addition reaction; a linear alkali-soluble resin containing a carboxy group in the main chain Resin; Resin in which an epoxy group-containing unsaturated compound is added to the carboxy group portion of a carboxy group-containing resin; (meth) acrylic resin; epoxy (meth) acrylate resin having a carboxy group, and the like. These can be used alone or in admixture of two or more.

  As the binder resin, a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer, a structural unit derived from (meth) acrylate and styrene, and a synthesis in which a (meth) acryl group is introduced into an epoxy resin A random copolymer containing a resin and a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from (meth) acrylate is preferred. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono ( And (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. That.

  The binder resin preferably has a total content of a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from (meth) acrylate of 50% by mass or more, more preferably 60% by mass or more, and still more preferably. 70% by mass or more. Further, the binder resin preferably has a structure content derived from a carboxy group-containing vinyl monomer of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 90% by mass or less. Is more preferable, and 70% by mass or less is more preferable.

  Among these, a random copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate is preferable. Specific examples of such a copolymer include a random copolymer of (meth) acrylic acid and butyl (meth) acrylate, a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate, (meth ) Random copolymers of acrylic acid, butyl (meth) acrylate and benzyl (meth) acrylate. From the viewpoint of the affinity between the binder resin and the colorant, the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.

  In the copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, and 10% by mass to 70% by mass in all monomer components. It is preferable that it is 20 mass%-70 mass%.

  The binder resin may have a carbon-carbon double bond capable of radical polymerization in the side chain. By having a double bond in the side chain, the photocurability of the colored composition according to the present invention is increased, so that the resolution and adhesion can be further improved. Examples of the method for introducing a radically polymerizable carbon-carbon double bond into the side chain include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p- ) A method of reacting a compound such as vinyl benzyl glycidyl ether with the acidic group of the binder resin.

  The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength and the like of the colored layer formed from the colored composition are improved, and when the Mw is 100,000 or less, the alkali developability of this coating film Is even better.

  The acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and still more preferably 90 mgKOH / g to 150 mgKOH / g. When the acid value of the binder resin is 20 mgKOH / g or more, the alkali developability when the colored composition is used as a colored layer is further improved, and when it is 170 mgKOH / g or less, the heat resistance is improved.

  The binder resin contained in the coloring composition may be only one type or a plurality of types. In the colored composition, the content of the binder resin is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the colorant, and 20 parts by mass. More preferably, it is 80 parts by mass.

(Crosslinking agent)
The coloring composition may contain a crosslinking agent. A cross-linking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. As the crosslinking agent, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable. The said crosslinking agent can be used individually or in mixture of 2 or more types.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional compound modified with caprolactone ( (Meth) acrylate, polyfunctional (meth) acrylate modified with alkylene oxide, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxy group and polyfunctional isocyanate, (meth) acrylate having hydroxy group And a polyfunctional (meth) acrylate having a carboxy group obtained by reacting an acid anhydride with the acid anhydride.

  Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; trivalent or more such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Of the aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Examples include pentaerythritol hexa (meth) acrylate and glycerol di (meth) acrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride; pyromellitic anhydride, biphenyltetracarboxylic acid And tetrabasic acid dianhydrides such as acid dianhydride and benzophenone tetracarboxylic dianhydride.

  In the colored composition of the present invention, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of the crosslinking agent is too large, the alkali developability of the colored composition of the present invention is lowered, and background stains, film residues, etc. tend to occur on the unexposed portion of the substrate or on the light shielding layer. .

(Photopolymerization initiator)
The colored composition preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator is a compound that generates active species capable of initiating polymerization of a crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far infrared light, electron beam, and X-ray.

  Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones. Compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. A photoinitiator can be used individually or in mixture of 2 or more types.

  In the colored composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, particularly preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing may be insufficient due to exposure. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

(Other ingredients)
If it is a range which does not impair the preferable physical property of this invention, another compounding agent other than the said compounding agent can be mix | blended with the said coloring composition. Other compounding agents include sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, organic carboxylic acids Acid anhydrides, pH adjusters, antioxidants other than the above-mentioned phenolic antioxidants, UV absorbers, light stabilizers, antiseptics, fungicides, anti-aggregation agents, adhesion improvers, development improvers, storage stability An agent etc. can be mentioned.

  As the sensitizing dye, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3 , 4-Diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- ( p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p -Diethylaminophenyl) benzothiazo 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) Examples include pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, and the like.

  Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.

  Nonionic surfactants include fluorosurfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra Fluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.) Surfactants, polyoxyethylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene Fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbite fatty acid esters And polyoxyethylene sorbite fatty acid esters).

Anionic surfactants include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, higher alcohol sulfate esters, aliphatic Alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surface activity Agents and the like.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like.
Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines and amino acids.

  Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.

  Organic carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid , Adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarbaryl acid, aconitic acid, benzoic acid, phthalic acid, etc. Examples thereof include carboxylic acids and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond.

  Examples of organic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- Examples include cyclohexene dicarboxylic acid, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.

<Manufacturing method of coloring composition and color filter>
The coloring composition can be prepared by mixing a dispersing agent composition, a coloring material, a dispersion medium, a binder resin, and, if necessary, a crosslinking agent, a photopolymerization initiator, and other additives. In addition, a coloring composition mixes (a) block copolymer, (b) aromatic compound, (c) tertiary amine compound, a coloring material, a dispersion medium, binder resin, and another component as needed. May be prepared. For the mixing, for example, a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader can be used. The coloring composition is preferably filtered after mixing. Examples of other additives include a pH adjuster, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiseptic, an antifungal agent, a surfactant, and an aggregation inhibitor.

  Since the coloring composition has alkali developability, it can be suitably used for a color filter.

  The color filter of this invention is provided with the colored layer formed using the said coloring composition. Examples of the method for producing the color filter include the following methods. First, thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins, polymethyl methacrylate resins, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, poly (meth) acrylic resins, various glasses, etc. For example, after applying the coloring composition of the present invention in which a red pigment is dispersed on the transparent substrate, pre-baking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkaline developer (an organic solvent or an aqueous solution containing a surfactant and an alkaline compound) to dissolve and remove unexposed portions of the coating film. To do. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement. Next, using each colored composition of green or blue, and applying each of the colored compositions, pre-baking, exposing, developing and post-baking in the same manner as described above, the green pixel array and the blue pixel array are formed on the same substrate. Sequentially formed on top. Thereby, a color filter in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

When applying the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. can be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.
A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film (ITO or the like) is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. A black matrix may be provided on a transparent substrate used to form a pixel array of the three primary colors of red, green, and blue.

The color filter of the present invention has high dimensional accuracy and can be suitably used for a color liquid crystal display element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, and the like.
In addition, since the colored composition has a low viscosity and the brightness of the coating film (colored body) formed from the colored composition is excellent, the colored composition is applied to the TFT substrate and the color filter substrate positioned with the liquid crystal layer interposed therebetween. It can be suitably used as a colored column spacer to be supported. For example, the composition of the high optical density (Optical Depth: OD) of Unexamined-Japanese-Patent No. 2015-191234 is mentioned.

  Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be implemented with appropriate modifications without departing from the scope of the invention. The polymerization rate, weight average molecular weight (Mw), molecular weight distribution (PDI), amine value and acid value of the dispersant and binder resin, and the viscosity and luminance of the colored composition were evaluated according to the following methods.

The abbreviations have the following meanings.
BTEE: ethyl-2-methyl-2-n-butylteranyl-propionate DBDT: dibutylditelluride AIBN: 2,2′-azobis (isobutyronitrile)
MMA: Methyl methacrylate BMA: Butyl methacrylate EHMA: 2-Ethylhexyl methacrylate BzMA: Benzyl methacrylate M4EGM: Methoxypolyethylene glycol monomethacrylate (trade name: Blemmer PME-200, manufactured by NOF Corporation)
DMAEMA: dimethylaminoethyl methacrylate BzCl: benzyl chloride MAA: methacrylic acid PI: phthalimide 2-NA: 2-naphthoic acid 2-NAOH: 2-naphthol 7-HC: 7-hydroxycoumarin 4-MU: 4-methylumbelliferone DBU: diazabicycloundecene DIPEA: diisopropylethylamine TEA: triethylamine PIDBU: phthalimide diazabicycloundecene PMA: propylene glycol monomethyl ether acetate MP: 1-methoxy-2-propanol

(Polymerization rate)
¹ H-NMR was measured (solvent: deuterated chloroform, internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) measuring apparatus (manufactured by Bruker, model: AVANCE500 (frequency: 500 MHz)). About the obtained NMR spectrum, the integration ratio of the monomer-derived vinyl group and the peak of the polymer-derived ester side chain was determined, and the polymerization rate of the monomer was calculated.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It calculated | required by the gel permeation chromatography (GPC) using the high performance liquid chromatograph (The Tosoh make, model: HLC8320). One column is SHODEX KF-603 (Φ6.0 mm × 150 mm) (manufactured by SHODEX), 30 mmol / L lithium bromide-30 mmol / L acetic acid-N-methylpyrrolidone is used as a mobile phase, and a differential refractive index detector is used as a detector. It was used. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 20 mg / mL, a sample injection amount of 10 μL, and a flow rate of 0.2 mL / min. A calibration curve (calibration curve) was prepared using polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630, 906) as a standard substance, and the weight average molecular weight ( Mw) and number average molecular weight (Mn) were measured. Molecular weight distribution (PDI = Mw / Mn) was calculated from these measured values.

(Amine number)
The amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of the solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
B = 56.11 × Vs × 0.1 × f / w
B: Amine value (mgKOH / g)
Vs: Amount of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration (mL)
f: 0.1 mol / L hydrochloric acid / 2-propanol solution titer w: mass (g) of measurement sample (in solid content)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. The measurement sample was dissolved in tetrahydrofuran, a few drops of phenolphthalein ethanol solution was added as an indicator, and neutralization titration was performed with a 0.1 mol / L potassium hydroxide / ethanol solution. The acid value (A) was calculated by the following formula.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L potassium hydroxide / ethanol solution used for titration (mL)
f: Potency of 0.1 mol / L potassium hydroxide / ethanol solution w: Mass (g) of measurement sample (solid content conversion)

(viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), a cone rotor (1 ° 34 ′ × R24) was used, and the viscosity was measured at 25 ° C. and a rotor rotational speed of 60 rpm.
After the preparation, the colored composition was stored at 25 ° C. for 2 hours, and then the viscosity was measured. Those having a viscosity of less than 10 mPa · s were evaluated as “A”, and those having a viscosity of 10 mPa · s or more were evaluated as “B”.

(Luminance)
A colored composition was applied to a glass plate, and after drying, a coating film was formed by heat treatment at 230 ° C. for 30 minutes to produce a colored glass. The colored glass plate was set in a spectrocolorimeter (trade name: CM-3700d, manufactured by Konica Minolta Sensing Co., Ltd.), and the transmission chromaticity at the XYZ coordinate axes in the C light source was measured. The Y value at this time was adopted as the luminance (Y). In Table 2, the brightness is measured by the coloring composition No. 1 to 8 are colored composition Nos. Evaluated with the brightness of the colored glass plate using 8 as a reference, the difference between the measured value and the reference value (measured value−reference value) is 0.4 or more, “A”, and the difference is more than 0 and less than 0.4 “B” and a difference of 0 were designated as “C”. In addition, the coloring composition No. 9 to 11 are colored composition Nos. 11 is evaluated based on the luminance of the colored glass plate, and the difference between the measured value and the reference value (measured value−reference value) is more than 0 and less than 0.2, and “A” is the difference and “B” is 0. did.

<Manufacture of block copolymer>
In a flask equipped with an argon gas introduction tube and a stirrer, MMA 46.1 g, BMA 22.2 g, EHMA 20.9 g, BzMA 15.4 g, M4EGM 8.1 g, MAA 8.1 g, AIBN 0.82 g, PMA 80. After charging 5 g and substituting with argon, 7.49 g of BTEE and 4.61 g of DBDT were added and reacted at 60 ° C. for 15 hours to polymerize the A block. The polymerization rate was 99%.

  A mixed solution of 54.3 g of DMAEMA, 0.41 g of AIBN, and 36.2 g of PMA, which had been substituted with argon in advance, was added to the reaction solution and reacted at 60 ° C. for 10 hours to polymerize the B block. The polymerization rate was 98%.

  After completion of the reaction, methanol (165 g) previously substituted with argon was added to the reaction solution for dilution, and 15.3 g of BzCl was added to the diluted solution, followed by reaction at 60 ° C. for 10 hours for quaternization.

  After completion of the reaction, the reaction solution was poured into n-heptane which was being stirred. The precipitated polymer was suction filtered and dried to obtain a block copolymer. The obtained block copolymer has an Mw of 7618, a PDI of 1.30, an acid value of 32 mgKOH / g, an amine value of 64 mgKOH / g, a content of A block in the copolymer of 63% by mass, and a B block. The content of 37% by mass, the content of the structural unit derived from the vinyl monomer having an acidic group in the copolymer is 4.3% by mass, and the structural unit represented by the general formula (1) in the copolymer And the total content rate of the structural unit represented by General formula (2) was 36.0 mass%. In addition, the content rate of each structural unit in a copolymer was computed from the charging rate of the vinyl monomer used for polymerization reaction, the polymerization rate of a vinyl monomer, and the reaction rate of the quaternizing agent used for the quaternization reaction.

<Preparation of dispersant composition>
(Dispersant composition No. A)
To a flask equipped with a stirrer, 87.5 g of a block copolymer, 8.91 g of PI, 9.23 g of DBU, 110 g of PMA, and 110 g of MP were added and heated and mixed at 60 ° C. for 20 hours to prepare a dispersant composition. .

(Dispersant composition No. B-H)
The composition of each component was changed as shown in Table 1, and the dispersant composition No. In the same manner as in the preparation method of A, the dispersant composition No. B to H were obtained.

<Preparation of coloring composition>
(Coloring composition No. 1)
Pigment (CI Pigment Green 58, trade name: FASTOGEN (registered trademark) GREEN A310, manufactured by DIC) 18 parts by weight, dispersant composition 12 parts by weight, alkali-soluble resin (trade name: Lipoxy (registered) (Trademark) SPC-2000, manufactured by Showa Polymer Co., Ltd.) 5.4 parts by mass and 64.6 parts by mass of PMA are put into a mixing tank having an internal volume of 500 ml, and stirred for 10 minutes at 2000 rpm using a disper to perform preliminary dispersion. It was. To the obtained preliminary dispersion, 640 parts by mass of zirconia beads having a diameter of 0.5 mm was added, and the mixture was stirred at 2000 rpm for 2 hours for main dispersion. To the obtained dispersion, 28.5 parts by mass of PMA was added, and further stirred at 1500 rpm for 10 minutes. The obtained final dispersion was filtered through a 2.5 μm mesh filter (trade name: HDC II Membrane Filter, manufactured by PALL) to remove zirconia beads. The viscosity and brightness of the obtained colored composition were evaluated. The results are shown in Table 2.

(Coloring composition Nos. 2 to 8)
Except that the dispersant was changed to that shown in Table 2, coloring composition No. In the same manner as in the preparation method of No. 1, coloring composition No. 2-8 were prepared. Coloring composition No. In No. 8, the block copolymer obtained above was used as a dispersant.

(Coloring composition No. 9)
Pigment (CI Pigment Blue 15: 6, trade name: FASTGEN (registered trademark) Blue A540, manufactured by DIC) 16 parts by weight, dispersant composition 24 parts by weight, alkali-soluble resin (trade name: Lipoxy) as binder resin (Registered trademark) SPC-2000, manufactured by Showa Polymer Co., Ltd.) 16 parts by mass and 44 parts by mass of PMA were put into a mixing tank having an internal volume of 500 ml, and stirred at 2000 rpm for 10 minutes using a disper for preliminary dispersion. To the obtained preliminary dispersion, 640 parts by mass of zirconia beads having a diameter of 0.5 mm was added, and the mixture was stirred at 2000 rpm for 2 hours for main dispersion. To the obtained dispersion, 33.3 parts by mass of PMA was added and further stirred at 1500 rpm for 10 minutes. The obtained final dispersion was filtered through a 2.5 μm mesh filter (trade name: HDC II Membrane Filter, manufactured by PALL) to remove zirconia beads. The viscosity and brightness of the obtained colored composition were evaluated. The results are shown in Table 2.

(Coloring composition 10-11)
Except that the dispersant was changed to that shown in Table 2, coloring composition No. In the same manner as in the preparation method of No. 9, the coloring composition no. 10 and 11 were prepared. Coloring composition No. In No. 11, the block copolymer obtained above was used as a dispersant.

  As a dispersant, dispersant composition No. A coloring composition No. using AH. Nos. 1 to 7, 9, and 10 have high dispersibility of the pigment and low viscosity. Among these, dispersant composition No. 1 containing a cyclic amidine compound as a tertiary amine compound. Colored composition No. using A to E and H. 1 to 5, 9, and 10 were excellent in the brightness of the coating film. That is, the coloring composition No. 1 to 5, 9, and 10 are excellent in discoloration resistance even when exposed to high temperatures in the manufacturing process of liquid crystal displays, and when a color filter is produced using these colored compositions, it can be expected that the luminance is improved. .

The present invention includes the following embodiments.
(Embodiment 1)
(A) A block including a structural unit derived from a vinyl monomer having an acidic group; a B unit including a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (B) at least one aromatic compound selected from the group consisting of aromatic dicarboxylic imides, acidic group-containing aromatic compounds and phenolic hydroxy group-containing aromatic compounds, and (c) ) A dispersant composition obtained by mixing a tertiary amine compound.

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In Formula (1), R <^11> , R < ¹² > and R < ¹³ > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

〔式（２）において、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹およびＲ²²が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²³は水素原子またはメチル基を示す。〕

[In Formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

(Embodiment 2)
The molar ratio of the quaternary ammonium base in the block copolymer (a) to the aromatic compound (b) (the quaternary ammonium base in (b) / (a)) is 0.5 to 1.2. The dispersant composition according to embodiment 1, wherein

(Embodiment 3)
The molar ratio of the quaternary ammonium base in the block copolymer (a) to the tertiary amine compound (c) (quaternary ammonium base in (c) / (a)) is 0.5 to 1. The dispersant composition according to embodiment 1 or 2, which is 2.

(Embodiment 4)
The dispersant composition according to any one of Embodiments 1 to 3, wherein the content of the structural unit derived from the vinyl monomer having an acidic group in the block copolymer (a) is 1% by mass to 20% by mass. object.

(Embodiment 5)
The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer (a) is 5% by mass to 50% by mass. The dispersant composition according to any one of aspects 1 to 4.

(Embodiment 6)
The dispersant according to any one of embodiments 1 to 5, wherein the (c) tertiary amine compound is a compound represented by the general formula (6) and / or a compound represented by the general formula (7). Composition.

〔一般式（６）において、Ｒ⁶¹、Ｒ⁶²およびＲ⁶³は、それぞれ独立して、置換基を有してもよい炭素数１〜１０の炭化水素基を示す。また、Ｒ⁶²およびＲ⁶³は互いに結合して環状構造を形成してよい。〕

[In General Formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁶² and R ⁶³ may combine with each other to form a cyclic structure. ]

〔一般式（７）において、Ｒ⁷¹は置換基を有してもよい炭素数２〜６の２価の炭化水素基を示し、Ｒ⁷²およびＲ⁷³は、それぞれ独立して、水素原子または置換基を有してもよい炭素数１〜１０の炭化水素基を示す。また、Ｒ⁷²およびＲ⁷³は互いに結合して環状構造を形成してよい。〕

[In the general formula (7), R ⁷¹ represents an optionally substituted divalent hydrocarbon group having 2 to 6 carbon atoms, and R ⁷² and R ⁷³ each independently represents a hydrogen atom or a substituent. The C1-C10 hydrocarbon group which may have a group is shown. R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure. ]

(Embodiment 7)
The coloring composition containing the dispersing agent composition, coloring material, dispersion medium, and binder resin as described in any one of Embodiments 1-6.

(Embodiment 8)
(A) A block including a structural unit derived from a vinyl monomer having an acidic group; a B unit including a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (B) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound, (c) 3 A colored composition comprising a mixture of a secondary amine compound, a colorant, a dispersion medium, and a binder resin.

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In Formula (1), R <^11> , R < ¹² > and R < ¹³ > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

〔式（２）において、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹およびＲ²²が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²³は水素原子またはメチル基を示す。〕

[In Formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

(Embodiment 9)
The colored composition according to embodiment 7 or 8, wherein the colorant is a phthalocyanine pigment.

(Embodiment 10)
The coloring composition as described in any one of Embodiments 7-9 which is an object for color filters.

(Embodiment 11)
A color filter comprising a colored layer formed using the colored composition according to the tenth embodiment.

  The block copolymer of this invention can be used as a dispersing agent of the coloring material of a coloring composition. The colored composition can be suitably used for a color filter. The color filter has high dimensional accuracy and can be suitably used for a color liquid crystal display element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, and the like.

Claims (11)

Colorants include phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, anthraquinone pigments, perylene pigments, and perinone pigments. A dispersant composition used for a coloring composition containing at least one selected from the group consisting of:
(A) A block including a structural unit derived from a vinyl monomer having an acidic group; a B unit including a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); A block copolymer having
(B) at least one aromatic compound selected from the group consisting of aromatic dicarboxylic imides, acidic group-containing aromatic compounds and phenolic hydroxy group-containing aromatic compounds, and
(C) Ri greens by mixing the tertiary amine compound,
The dispersant composition, wherein the (c) tertiary amine compound is a compound represented by the general formula (6) and / or a compound represented by the general formula (7).

[In Formula (1), R <^11> , R < ¹² > and R < ¹³ > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

[In Formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

[In General Formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁶² and R ⁶³ may combine with each other to form a cyclic structure. ]

[In the general formula (7), R ⁷¹ represents an optionally substituted divalent hydrocarbon group having 2 to 6 carbon atoms, and R ⁷² and R ⁷³ each independently represents a hydrogen atom or a substituent. The C1-C10 hydrocarbon group which may have a group is shown. R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure. ]   The molar ratio of the quaternary ammonium base in the block copolymer (a) to the aromatic compound (b) (the quaternary ammonium base in (b) / (a)) is 0.5 to 1.2. The dispersant composition according to claim 1.   The molar ratio of the quaternary ammonium base in the block copolymer (a) to the tertiary amine compound (c) (quaternary ammonium base in (c) / (a)) is 0.5 to 1. The dispersant composition according to claim 1, which is 2.   The content rate of the structural unit derived from the vinyl monomer which has an acidic group in the said (a) block copolymer is 1 mass%-20 mass%, Dispersant composition as described in any one of Claims 1-3. object.   The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer (a) is 5% by mass to 50% by mass. Item 5. The dispersant composition according to any one of Items 1 to 4. The dispersing agent composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (7) is a compound represented by the general formula (8).

[In general formula (8), R ⁸⁰ ~ R ⁸⁹ Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n is an integer of 1 to 4. m is an integer of 1-4. ] Containing the dispersant composition, colorant, dispersion medium and binder resin according to any one of claims 1 to 6 ,
The colorant is a phthalocyanine pigment, isoindolinone pigment, isoindoline pigment, quinacridone pigment, indigo pigment, thioindigo pigment, quinophthalone pigment, anthraquinone pigment, perylene pigment, and perinone pigment. A coloring composition comprising at least one selected from the group consisting of: (A) A block including a structural unit derived from a vinyl monomer having an acidic group; a B unit including a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); (B) at least one aromatic compound selected from the group consisting of an aromatic dicarboxylic imide, an acidic group-containing aromatic compound, and a phenolic hydroxy group-containing aromatic compound, (c) 3 grade amine compounds, colorants, Ri Na were mixed dispersion medium and a binder resin,
The (c) tertiary amine compound is a compound represented by the general formula (6) and / or a compound represented by the general formula (7),
The colorant is a phthalocyanine pigment, isoindolinone pigment, isoindoline pigment, quinacridone pigment, indigo pigment, thioindigo pigment, quinophthalone pigment, anthraquinone pigment, perylene pigment, and perinone pigment. A coloring composition comprising at least one selected from the group consisting of:

[In Formula (1), R <^11> , R < ¹² > and R < ¹³ > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents a counter ion. ]

[In Formula (2), R ²¹ and R ²² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group. ]

[In General Formula (6), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. R ⁶² and R ⁶³ may combine with each other to form a cyclic structure. ]

[In the general formula (7), R ⁷¹ represents an optionally substituted divalent hydrocarbon group having 2 to 6 carbon atoms, and R ⁷² and R ⁷³ each independently represents a hydrogen atom or a substituent. The C1-C10 hydrocarbon group which may have a group is shown. R ⁷² and R ⁷³ may be bonded to each other to form a cyclic structure. ]   The coloring composition according to claim 7 or 8, wherein the coloring material is a phthalocyanine pigment.   The coloring composition as described in any one of Claims 7-9 which is an object for color filters.   A color filter comprising a colored layer formed using the colored composition according to claim 10.