JP6316531B1 - Block copolymer, dispersant and pigment dispersion composition - Google Patents

Abstract

A block copolymer that can be used as a dispersant and has excellent heat resistance is provided. 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 following general formula (1), and a general formula (2). And a B block including a structural unit. [In the formulas (1) and (2), R11, R12, R13, R21 and R22 each independently represent 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. X1 and X2 each represent a divalent linking group. R14 and R23 each represents a hydrogen atom or a methyl group. Y- represents at least one selected from the group consisting of an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, and an aromatic carboxylic acid anion. ] [Selection figure] None

Description

  The present invention relates to a block copolymer, a dispersant, and a pigment dispersion 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 color 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 pigment dispersion composition in which a pigment, a dispersant, and a dispersion medium (solvent) are mixed is formed on a substrate, exposed through a photomask having a desired pattern shape, and alkali developed. Is done.

  In the production of a liquid crystal display, after forming a color material pattern shape, a transparent electrode for driving the liquid crystal is formed thereon by vapor deposition or sputtering, and further an orientation for aligning the liquid crystal in a certain direction. A film is formed. In order to obtain sufficient performance of these transparent electrodes and alignment films, their formation is generally performed at a high temperature of 200 ° C. or higher. However, when a large amount of resin-type dispersant is used in the pigment dispersion composition, heat resistance such as a decrease in contrast ratio of the color filter and a change in hue becomes a problem before and after the process involving high heat.

  Therefore, resin-type dispersants with improved heat resistance have been proposed. For example, in Patent Document 1, in order to obtain a color filter having excellent heat resistance, an AB block comprising an A block having a quaternary ammonium base in the side chain and a B block not having a quaternary ammonium base. It is disclosed that a copolymer is used as a pigment dispersant for a color filter (see Patent Document 1 (Claim 1, paragraphs 0049 to 0058)).

  In Patent Document 2, an AB block copolymer comprising an A block having an acidic group in the side chain and a B block having an amino group or a quaternary ammonium base in the side chain is used as a pigment dispersant. It is disclosed that coating properties, long-term storage stability, and alkali developability are improved (see Patent Document 2 (Claim 1, paragraphs 0031 to 0034 and 0038 to 0040)).

JP 2012-068559 A JP 2013-203887 A

  Conventionally, resin type dispersants with improved heat resistance have been proposed, but there has been a problem that the heat resistance of the resin type dispersants is not sufficient. The present invention has been made in view of the above circumstances, and an object thereof is to provide a block copolymer that can be used as, for example, a dispersant and has excellent heat resistance.

  The block copolymer of the present invention that has been able to solve the above-mentioned problems includes 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), and a general formula ( And a B block including the structural unit represented by 2).

〔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^-は芳香族ジカルボン酸イミドアニオン、芳香族スルホン酸アニオン、芳香族ホスホン酸アニオンおよび芳香族カルボン酸アニオンよりなる群から選択される少なくとも１種を示す。〕

[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 at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion. ]

〔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. ]

  Conventional polymers having a quaternary ammonium base generally use a halogen anion as a counter ion of a quaternary ammonium cation. Such a polymer containing a halogen anion is considered to be inferior in heat resistance because it causes a counterion elimination reaction in a high temperature atmosphere. In the block copolymer of the present invention, since the counter ion of the quaternary ammonium cation in the B block is an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, or an aromatic carboxylic acid anion, Excellent in properties. Moreover, since the block copolymer of this invention has A block which has an acidic group, and B block which has a specific structure, it can be used as a dispersing agent.

  The block copolymer is preferably an AB type block copolymer. In the block copolymer, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 2% by mass to 20% by mass in 100% by mass of the A block. In the block copolymer, the content of the structural unit represented by the general formula (1) is preferably 30% by mass to 85% by mass in 100% by mass of the B block. The content of the A block is preferably 35% by mass to 85% by mass in 100% by mass of the block copolymer.

  The present invention also includes a first composition containing the block copolymer, and a second composition obtained by washing the first composition with water and drying. The molecular weight distribution (PDI) of the block copolymer contained in the first composition is preferably 2.0 or less. Moreover, the dispersing agent containing the said block copolymer, a 1st composition, or a 2nd composition is contained in this invention. Furthermore, the present invention includes a pigment dispersion composition containing the dispersant, a pigment, and a dispersion medium. Examples of such a composition include a pigment dispersion composition for a color filter.

  The production method of the block copolymer of the present invention 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 following formula (2), and the following formula (3). A step (A) of preparing a block copolymer precursor having a B block containing a structural unit, and a precursor of the block copolymer obtained in the step (A), an aromatic dicarboxylic imide, an aromatic And a step (B) of obtaining a block copolymer by reacting at least one alkali metal salt selected from the group consisting of aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids.

〔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. ]

〔式（３）において、Ｒ³¹、Ｒ³²およびＲ³³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。Ｒ³¹、Ｒ³²およびＲ³³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。Ｘ³は２価の連結基を示す。Ｒ³⁴は水素原子またはメチル基を示す。Ｘ^-はハロゲンアニオンを示す。〕

[In the formula (3), R ³¹ , R ³² and R ³³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁻ represents a halogen anion. ]

  In the step (B), an aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid or an alkali metal salt of aromatic carboxylic acid is used to convert the counter ion of the quaternary ammonium cation from the halogen anion to the aromatic dicarboxylic acid. It becomes easy to exchange (anion exchange) with an acid imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion or an aromatic carboxylate anion.

  Regarding the anion exchange in this step (B), each ion is classified based on the HASB rule. For example, halide ions (eg, chloride ions) are classified as hard bases because of their high electronegativity and low polarizability. Alkali metal ions (eg, potassium ions) are classified as hard acids. Aromatic dicarboxylic imide anions, aromatic sulfonate anions, aromatic phosphonate anions and aromatic carboxylate anions having a π-electron system of aromatic rings are considered to be classified as soft bases. Quaternary ammonium ions in the polymer are considered to be classified as soft acids. According to the HSAB rule, it is said that a combination of an acid and a base having the same degree of hardness, such as a soft base for a soft acid and a hard base for a hard acid, has a strong binding force. It is considered that the anion exchange is facilitated by generating an ion pair having a strong binding force in the anion exchange.

  In the production method, the block copolymer precursor is preferably prepared by using living radical polymerization in the step (A). The production method preferably includes a step (C) of washing the block copolymer obtained in the step (B) with water.

  According to the present invention, for example, a block copolymer that can be used as a dispersant and has excellent heat resistance can be provided.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

<1 block copolymer>
The block copolymer of the present invention 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 a 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”.

  Various components of the block copolymer of the present invention will be described below.

(1.1 A block)
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 in a pigment dispersion 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 and the like.

  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, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine and the like.
Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-captolactam 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 polyethylene glycol structural unit; (meth) acrylate having a hydroxy group; caprolactone adduct of (meth) acrylate having a hydroxy group; ) Acrylate; (meth) acrylate having a cyclic ether group.

  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 polyethylene glycol structural unit include polyethylene glycol (n = 1-5) methyl ether (meth) acrylate, polyethylene glycol (n = 1-5) ethyl ether (meth) acrylate,
Polyethylene glycol (n = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1-5) ethyl ether (meth) acrylate, polypropylene glycol (N = 1-5) propyl ether (meth) acrylate etc. are mentioned.

  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.

  As the caprolactone adduct of (meth) acrylate having a hydroxy group, 1 mol of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2 mol of caprolactone adduct of 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) Examples include acrylate caprolactone 3 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 5 mol adduct, and the like.

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

  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, polyethylene glycol structure At least one selected from the group consisting of (meth) acrylates having units, (meth) acrylates having hydroxy groups, caprolactone adducts of (meth) acrylates having hydroxy groups, and (meth) acrylates having cyclic ether groups More preferably. 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 When the structural unit is derived, the total content of these structural units is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more in 100% by mass of the A block. 98 mass% or less is preferable, More preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less.

  A block is (meth) acrylamide, (meth) acrylate having a polyethylene glycol structural unit, (meth) acrylate having a hydroxy group, caprolactone adduct of (meth) acrylate having a hydroxy group, (meth) acrylate having an alkoxy group And having 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 100% by mass in the A block. 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, and further preferably 60% by mass or less. .

  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, when used as a pigment dispersant, the pigment is adsorbed by both the A block and the B block, and the dispersion performance of the pigment is lowered. 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.

(1.2 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 a tertiary amino group, it is considered to have a high affinity with the pigment.

(1.2.1 Structural unit represented by general formula (1))
The structural unit represented by the general formula (1) has a quaternary ammonium salt in the structure, and as its anion component, an aromatic dicarboxylic acid imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion and an aromatic It has at least one selected from the group consisting of carboxylate anions. 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^-は芳香族ジカルボン酸イミドアニオン、芳香族スルホン酸アニオン、芳香族ホスホン酸アニオンおよび芳香族カルボン酸アニオンよりなる群から選択される少なくとも１種を示す。〕

[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 at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion. ]

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 (11-1), (11-2), and (11-3).

〔一般式（１１−１）、（１１−２）、（１１−３）において、Ｒ⁶¹は、Ｒ¹¹〜Ｒ¹³のいずれかである。Ｒ⁶²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。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ⁶²は、それぞれ同一でも異なっていてもよい。〕

[In General Formulas (11-1), (11-2), and (11-3), R ⁶¹ is any one of R ^{11 to} R ¹³ . R ⁶² 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. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ⁶² may be the same or different. ]

In the general formula (1), examples of the divalent linking group X ¹ include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ¹⁵ — group, a —COO—R ¹⁶ — group [ R ¹⁵ and R ¹⁶ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms]. The divalent linking group X ¹ is preferably a —COO—R ¹⁶ — group, more preferably a —COO—R ¹⁷ — group (wherein R ¹⁷ is a methylene group or an alkylene group having 2 to 4 carbon atoms). .

In the general formula (1), Y ⁻ as a counter ion represents at least one selected from the group consisting of an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, and an aromatic carboxylic acid anion. These in any counterion Y ^- is an aromatic dicarboxylic acid imide anion, an aromatic sulfonate anion is preferred.

  The aromatic dicarboxylic imide anion is an anion of an aromatic dicarboxylic imide and is obtained by removing protons from nitrogen constituting the dicarboimide. The aromatic dicarboxylic 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. As the aromatic dicarboxylic acid imide anion, those represented by the general formula (12) are preferable.

〔一般式（１２）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 (12), Ring A represents an aromatic ring which may have a substituent. ]

  In the general formula (12), 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. 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.

  Examples of the aromatic dicarboxylic acid imide anion include 1,3-dioxo-1,3-dihydro-2H-isoindole-2-ide (formula (12-1)); 1,3-dioxo-1,3-dihydro- 2H-benzo [f] isoindole-2-id (formula (12-2)); 1,3-dioxo-1,3-dihydro-2H-benzo [g] isoindole-2-ide (formula (12- 3)); 5-phenyl-1,3-dioxo-1,3-dihydro-2H-isoindole-2-ide (formula (12-4)); 1,3-dioxo-1,3-dihydro-2H -Naphtho [2,3-f] isoindole-2-oid (formula (12-5)); 1,3-dioxo-1,3-dihydro-2H-naphtho [2,3-g] isoindole-2 -Id (formula (12-6)); 1,3-dioxo-1,3-dihi B -2H- dibenzo [e, g] isoindol-2-Id (formula (12-7)); and the like.

  The aromatic sulfonate anion is an anion of an aromatic sulfonate. The aromatic sulfonic acid has an aromatic ring and a sulfonic acid group directly bonded to the aromatic ring in the molecule. As an aromatic sulfonate anion, what is represented by following formula (13) is preferable.

〔一般式（１３）において、Ａｒは置換基を有していてもよい芳香環を表す。〕

[In General formula (13), Ar represents the aromatic ring which may have a substituent. ]

  In the general formula (13), the aromatic ring constituting Ar 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. 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.

  As aromatic sulfonate anions, benzenesulfonate anion (formula (13-1)); 1-naphthalenesulfonate anion (formula (13-2)); 2-naphthalenesulfonate anion (formula (13-3)) 4-biphenylsulfonate anion (formula (13-4)); 2-anthracenesulfonate anion (formula (13-5)); 1-anthracenesulfonate anion (formula (13-6)); 3-phenanthrenesulfone Acid anion (formula (13-7)); p-styrene sulfonate anion (formula (13-8)); p-toluene sulfonate anion (formula (13-9)) and the like.

  An aromatic phosphonic acid anion is an anion of an aromatic phosphonic acid. Aromatic phosphonic acids have an aromatic ring and a phosphonic acid group directly bonded to the aromatic ring in the molecule. As an aromatic phosphonate anion, what is represented by following formula (14) is preferable.

〔一般式（１４）において、Ａｒは置換基を有していてもよい芳香環を表す。〕

[In General formula (14), Ar represents the aromatic ring which may have a substituent. ]

  In the general formula (14), the aromatic ring constituting Ar 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. 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.

  As aromatic phosphonate anions, benzenephosphonate anion (formula (14-1)); 1-naphthalenephosphonate anion (formula (14-2)); 2-naphthalenephosphonate anion (formula (14-3)) 4-biphenylphosphonate anion (formula (14-4)); 2-anthracenephosphonate anion (formula (14-5)); 1-anthracenephosphonate anion (formula (14-6)); 3-phenanthrenephosphone Acid anion (formula (14-7)); and the like.

  The aromatic carboxylate anion is an anion of an aromatic carboxylate. The aromatic carboxylic acid has an aromatic ring and a carboxy group directly bonded to the aromatic ring in the molecule. As an aromatic carboxylate anion, what is represented by following formula (15) is preferable.

〔一般式（１５）において、Ａｒは置換基を有していてもよい芳香環を表す。〕

[In General formula (15), Ar represents the aromatic ring which may have a substituent. ]

  In the general formula (15), the aromatic ring constituting Ar 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. 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.

  Examples of the aromatic carboxylate anion include benzoate anion (formula (15-1)); 1-naphthalenecarboxylate anion (formula (15-2)); 2-naphthalenecarboxylate anion (formula (15-3)); 4-biphenylcarboxylate anion (formula (15-4)); 2-anthracenecarboxylate anion (formula (15-5)); 1-anthracenecarboxylate anion (formula (15-6)); 3-phenanthrenecarboxylic acid Anion (formula (15-7)); p-styrenecarboxylic acid anion (formula (15-8)); p-toluenecarboxylic acid anion (formula (15-9)) 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, and still more preferably 75% 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 pigment has high affinity with the pigment.

(1.2.2 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 (21-1), (21-2), and (21-3).

〔一般式（２１−１）、（２１−２）、（２１−３）において、Ｒ⁷¹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。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ⁷¹は、それぞれ同一でも異なっていてもよい。〕

[In General Formulas (21-1), (21-2), and (21-3), R ⁷¹ 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. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ⁷¹ may be the same or different. ]

In the general formula (2), examples of the divalent linking group X ² include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ²⁴ — group, and a —COO—R ²⁵ — group. [Wherein R ²⁴ and R ²⁵ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms]. A COO—R ²⁵ — group, more preferably a —COO—R ²⁶ — group (wherein R ²⁶ is a methylene group or an alkylene group having 2 to 4 carbon atoms).

  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 70% by mass in 100% by mass of the B block. % Or less, more preferably 65% by mass or less, and still more preferably 60% by 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 pigment has high affinity with the pigment.

  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 pigment, 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. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more. Moreover, it is preferable that B block does not contain substantially the structural unit derived from the vinyl monomer which has the acidic group which A block has. That is, the content of the structural unit derived from the vinyl monomer having an acidic group in the A block is preferably 5% by mass or less, and more preferably 2% 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.

(1.3 Block copolymer)
The structure of the block copolymer of the present invention 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, so that the pigment, the solvent, and the binder resin (alkali-soluble resin) can be efficiently operated suitably.

  The content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 85% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 80 mass% or less, More preferably, it is 75 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 preferably 65% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 60 mass% or less, More preferably, it is 55 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.

<First composition of 2 block copolymer>
The first composition of the present invention contains the block copolymer. The first composition contains components other than the block copolymer. As said other component, the impurity resulting from the manufacturing method of a block copolymer is mentioned. For example, in the production of a block copolymer, at least one alkali selected from the group consisting of a quaternizing agent described later, aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid is used. When a metal salt is used, examples include a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide. The first composition is prepared by filtering impurities such as precipitated salts (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as aromatic dicarboxylic acid imide). It is preferable to remove.

  The molecular weight of the block copolymer contained in the first composition is measured by a gel permeation chromatography (hereinafter referred to as “GPC”) method. The block copolymer preferably has a weight average molecular weight (Mw) of 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 or less. . 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 block copolymer contained in the first composition is preferably 2.0 or less, more preferably 1.6 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. 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.

  The amine value of the first composition is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and 200 mgKOH / g from the viewpoint of the adsorptivity to the pigment and the pigment dispersibility. g or less is preferable, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.

  The acid value of the first composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less. By setting the acid value within this range, the binder resin (alkali-soluble resin) can be suitably acted on without impairing the affinity of the block copolymer with the pigment.

<Second composition of 3-block copolymer>
The second composition of the present invention is obtained by washing the first composition with water and drying. The second composition after washing and drying has a reduced content of salt (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide). Has been. In addition, about the 2nd composition, the impurity resulting from the manufacturing method of a block copolymer is contained like the said 1st composition. The said 1st composition is a composition containing the said block copolymer, and the reaction liquid at the time of synthesize | combining a block copolymer is also contained.

  The block copolymer contained in the second composition may or may not have the structural unit represented by the general formula (1). Moreover, said 2nd composition contains other components other than a block copolymer. Examples of the other components include aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids. These aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids may be anions or alkali metal salts.

  The molecular weight of the block copolymer contained in the second composition is measured by a GPC method. The block copolymer preferably has a weight average molecular weight (Mw) of 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 or less. . 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 block copolymer contained in the second composition is preferably 2.0 or less, and more preferably 1.6 or less. 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.

  The amine value of the second composition is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and 200 mgKOH / g from the viewpoint of the adsorptivity to the pigment and the pigment dispersibility. g or less is preferable, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.

  The acid value of the second composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less.

  The second composition preferably has a halogen anion content of 8000 ppm or less, more preferably 6000 ppm or less, and still more preferably 4000 ppm or less.

<Method for producing 4 block copolymer>
The method for producing a block copolymer of the present invention comprises an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (2) described later, and a general formula (3) described later. A step (A) of preparing a block copolymer precursor having a B block containing a structural unit represented by formula (1): an aromatic dicarboxylic acid as a precursor of the block copolymer obtained in the step (A); A step (B) of obtaining a block copolymer by reacting at least one alkali metal salt selected from the group consisting of imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid. And In the present invention, the “block copolymer precursor” refers to a block copolymer before anion exchange.

(4.1 Step (A))
In the step (A), a block copolymer precursor is prepared. The block copolymer precursor includes an A block including a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (2), and a structural unit represented by the general formula (3). B block including

〔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. ]

R ^{21 to} R ²³ and X ² in the formula (2) are the same as those described in the description of the above (B block).

〔式（３）において、Ｒ³¹、Ｒ³²およびＲ³³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。Ｒ³¹、Ｒ³²およびＲ³³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。Ｘ³は２価の連結基を示す。Ｒ³⁴は水素原子またはメチル基を示す。Ｘ^-はハロゲンアニオンを示す。〕

[In the formula (3), R ³¹ , R ³² and R ³³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁻ represents a halogen anion. ]

The chain hydrocarbon group represented by R ^{31 to} R ³³ includes both linear and branched chains. Examples of the substituent that the chain hydrocarbon group represented by R ^{31 to} R ³³ 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 ^{31 to} R ³³ has include a chain alkyl group, a halogen group, an alkoxy group, and a hydroxy group.

Examples of the group represented by R ^{31 to} R ³³ 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 are more preferable.

Examples of the cyclic structure formed by bonding two or more of R ^{31 to} R ³³ 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 (31-1), (31-2), and (31-3).

〔一般式（３１−１）、（３１−２）、（３１−３）において、Ｒ⁸¹は、Ｒ³¹〜Ｒ³³のいずれかである。Ｒ⁸²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。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ⁸²は、それぞれ同一でも異なっていてもよい。〕

[Formula (31-1), (31-2), in (31-3), R ⁸¹ is either R ³¹ to R ^33. R ⁸² 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. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ⁸² may be the same or different. ]

In the general formula (3), examples of the divalent linking group X ³ include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ³⁵ — group, and a —COO—R ³⁶ — group. [Wherein R ³⁵ and R ³⁶ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms]. A COO—R ³⁶ — group, more preferably a —COO—R ³⁷ — group (wherein R ³⁷ is a methylene group or an alkylene group having 2 to 4 carbon atoms).

Examples of X ⁻ include halogen anions such as chloride ion, bromide ion and iodide ion, and chloride ion is preferable.

(4.1.1 A block)
In the step (A), the A block can be obtained, for example, by polymerizing a monomer composition containing a vinyl monomer having an acidic group.

  As the vinyl monomer having an acidic group used in the step (A), those described above can be used, and are selected from a vinyl monomer having a carboxy group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphate group. At least one of these is preferred. Moreover, in addition to the vinyl monomer which has an acidic group, you may mix | blend the vinyl monomer which can form the other structural unit of A block mentioned above with the monomer composition for A block.

(4.1.2 B block)
In the step (A), the B block is a monomer containing a vinyl monomer that can form the structural unit represented by the general formula (2) and a vinyl monomer that can form the structural unit represented by the general formula (3). A method of polymerizing the composition; after polymerizing a monomer composition containing a vinyl monomer capable of forming the structural unit represented by the general formula (2), the polymer is represented by the general formula (2) in the obtained polymer. And a method of quaternizing a tertiary amine structure of a part of the structural unit.

  Although it does not specifically limit as a vinyl monomer which can form the structural unit represented by the said General formula (2), For example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) Examples include acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, and the like. The vinyl monomer that can form the structural unit represented by the general formula (2) may be used alone or in combination of two or more.

  The vinyl monomer that can form the structural unit represented by the general formula (3) is not particularly limited. For example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meta ) Acryloyloxybutyltrimethylammonium chloride, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride Chloride, (meth) acryloyloxypropylbenzyldiethylammonium chloride, (meth) acryloyl (Meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium bromide, (meta) ) Acryloyloxypropylbenzyldimethylammonium bromide, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, (meth) acryloyloxybutylbenzyldiethyl Ammonium bromide (Meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) acryloyloxybutyltrimethylammonium iodide, (meth) acryloyloxyethylbenzyldimethylammonium iodide, (meth) acryloyloxy Propylbenzyldimethylammonium iodide, (meth) acryloyloxybutylbenzyldimethylammonium iodide, (meth) acryloyloxyethylbenzyldiethylammonium iodide, (meth) acryloyloxypropylbenzyldiethylammonium iodide, (meth) acryloyloxybutylbenzyl Diethylammonium iodide; (meth) acryloyloxyethyltrimethylammo Nium fluoride, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxyethylbenzyldimethylammonium fluoride, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) Examples thereof include acryloyloxybutylbenzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyldiethylammonium fluoride, (meth) acryloyloxypropylbenzyldiethylammonium fluoride, and (meth) acryloyloxybutylbenzyldiethylammonium fluoride. The vinyl monomer capable of forming the structural unit represented by the general formula (3) may be used alone or in combination of two or more.

  In addition, when the tertiary amine structure of the structural unit represented by the general formula (2) is quaternized, the quaternizing agent includes alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, etc. An aralkyl halide such as benzyl chloride, benzyl bromide or benzyl iodide; Among these, aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide are preferable, and benzyl chloride is more preferable. 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 general formula (3) can be estimated by measuring the amount of the alkyl group and aralkyl group introduced by quaternization.

(4.1.3 Method)
As the step (A), a method of first producing an A block and polymerizing a monomer of a B block into the A block; a method of producing a B block first and polymerizing a monomer of the A block into the B block; A method in which the A block and the B block are coupled after the A block and the B block are manufactured separately; the vinyl that can form the structural unit represented by the general formula (2) in the A block by first manufacturing the A block A method of polymerizing a monomer composition containing a monomer and quaternizing a tertiary amine structure of a part of the structural unit represented by the general formula (2) in the obtained polymer; A monomer composition containing a vinyl monomer capable of forming the structural unit represented is polymerized, and a monomer of an A block is polymerized to this polymer, and the structure represented by the general formula (2) in the obtained polymer Part 3 of the unit A method for quaternizing a min structure; A block and a block having a structural unit represented by the general formula (2) are separately produced, and after coupling these blocks, And a method of quaternizing part of the tertiary amine structure of the structural unit represented by the formula (2).

(4.1.4 Living radical polymerization)
The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the first block copolymer is preferably polymerized using 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. While the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, the termination reaction and chain transfer are unlikely to occur, and the growth end grows without being deactivated. This is preferable in that it is easy to produce a polymer having a uniform composition.

  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 is a method to be used (TERP method). Since the ATRP method uses an amine-based complex, it may not be used unless the acidic group of the vinyl monomer having an acidic group is protected. 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 viewpoints 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 method in which a vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (4).
(B) A method in which a vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (4) and an azo polymerization initiator.
(C) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4) and an organic ditellurium compound represented by the general formula (5).
(D) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4), an azo polymerization initiator, and an organic ditellurium compound represented by the general formula (5).

〔一般式（４）において、Ｒ⁴¹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。Ｒ⁴²およびＲ⁴³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。Ｒ⁴⁴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。〕

In [Formula (4), R ⁴¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. R ⁴² and R ⁴³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴⁴ 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. ]

〔一般式（５）において、Ｒ⁴¹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 [Formula (5), R ⁴¹ represents an alkyl group, an aryl group or an aromatic heterocyclic group having 1 to 8 carbon atoms. ]

The group represented by R ⁴¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, and 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.
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 ⁴² and R ⁴³ 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 ⁴⁴ 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 a 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 ⁴⁴¹ (R ⁴⁴¹ is a carbon number) 1-8 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.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tet- A butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like can be given.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include —CONR ⁴⁴²¹ R ⁴⁴²² (R ⁴⁴²¹ and R ⁴⁴²² 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 ⁴⁴³ (R ⁴⁴³ 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, ter-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.
As the allyl group, —CR ⁴⁴⁴¹ R ⁴⁴⁴² —CR ⁴⁴⁴³ = CR ⁴⁴⁴⁴ R ⁴⁴⁴⁵ (R ⁴⁴⁴¹ and R ⁴⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴⁴³ , R ⁴⁴⁴⁴ and R ⁴⁴⁴⁵ are Are each independently 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 ⁴⁴⁵¹ R ⁴⁴⁵² —C≡CR ⁴⁴⁵³ (R ⁴⁴⁵¹ and R ⁴⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴⁵³ 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 (4) 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-propinate, 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 Illustrate all tellurium compounds It is possible.

  Specific examples of the organic ditellurium compound represented by the general formula (5) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, Di-n-butylditelluride, di-s-butylditelluride, di-t-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, Examples thereof include bis- (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) propyl Pan], 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 (4). An azo polymerization initiator and / or an organic ditellurium compound of the general formula (5) is mixed. At this time, examples of the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferable.

  In the polymerization methods (a), (b), (c) and (d), the amount of vinyl monomer used may be appropriately adjusted depending on the physical properties of the target copolymer. The vinyl monomer is preferably 5 to 10,000 mol per mol of the organic tellurium compound.

  In the polymerization method (b), when the organic tellurium compound of the general formula (4) and the azo polymerization initiator are used in combination, the amount of the azo polymerization initiator used is usually an organic compound of the general formula (4). The azo polymerization initiator is preferably 0.01 mol to 10 mol with respect to 1 mol of the tellurium compound.

  In the polymerization method (c), when the organic tellurium compound of the general formula (4) and the organic ditellurium compound of the general formula (5) are used in combination, The organic ditellurium compound of the general formula (5) is preferably 0.01 mol to 100 mol per 1 mol of the organic tellurium compound of the general formula (4).

  In the polymerization method (d), when the organic tellurium compound of the general formula (4), the organic ditellurium compound of the general formula (5) and the azo polymerization initiator are used in combination, Usually, the azo polymerization initiator is preferably 0.01 to 100 mol with respect to 1 mol in total of the organic tellurium compound of the general formula (4) and the organic ditellurium compound of the general formula (5).

  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 benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, Examples include carbon chloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluoromethylbenzene. 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 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 growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ⁴¹ (wherein R ⁴¹ is the same as described above), and it is deactivated by the operation in the air after the completion of the polymerization reaction. , 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 tellurium atoms, 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 .; Method of adsorbing metal: Add peroxide such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose tellurium atoms at the end of the copolymer. A liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less can be used. These methods can also be used in combination.

(4.1.5 Quaternization)
As a method of quaternizing a tertiary amine structure of a part of the structural unit represented by the general formula (2) in the polymer, a method of bringing the polymer into contact with a quaternizing agent can be mentioned. Specifically, after polymerizing a monomer composition containing a vinyl monomer that can form the structural unit represented by the general formula (2), a quaternizing agent is added to the reaction solution, followed by stirring. It is done.

  The temperature of the reaction solution to which the quaternizing agent is added is preferably 55 ° C. to 65 ° C., and the stirring time is preferably 5 hours to 20 hours. When adding the quaternizing agent, it is also preferable to dilute the reaction solution after polymerization. Examples of the solvent to be added for dilution include a solvent that can be used for the polymerization reaction, a protic solvent is preferable, and methanol is more preferable.

(4.1.6 Block copolymer precursor)
The molecular weight of the block copolymer precursor is measured by the GPC method. The weight average molecular weight (Mw) of the block copolymer precursor 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.

  The molecular weight distribution (PDI) of the block copolymer precursor is preferably 2.0 or less, and more preferably 1.6 or less.

  The content of A block in the block copolymer precursor is preferably 35% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more in 100% by mass of the entire block copolymer. Yes, 85 mass% or less is preferable, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. The content of B block in the block copolymer precursor is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more, in 100% by mass of the entire block copolymer. Yes, 65 mass% or less is preferable, More preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less.

  The amine value of the block copolymer precursor is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and still more preferably 30 mgKOH / g or more, from the viewpoints of adsorptivity to pigment and pigment dispersibility. 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less. The amine value of the block copolymer precursor is derived from the structural unit represented by the general formula (2).

  The acid value of the precursor of the block copolymer is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g. g or less, more preferably 35 mgKOH / g or less.

(4.2 Step (B))
In the step (B), after completion of the step (A), the precursor of the obtained block copolymer is selected from the group consisting of aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid. At least one alkali metal salt is allowed to act to obtain a block copolymer. By the step (B), the halogen anion of the structural unit represented by the general formula (3) is exchanged for an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonium ion, or an aromatic carboxylate anion (anion). Exchange).

  Examples of the alkali metal in at least one alkali metal salt selected from the group consisting of aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid include lithium, sodium, potassium, rubidium, cesium, There is francium, and among these, lithium, sodium, and potassium are preferable because of economical advantages.

  Examples of the alkali metal salt of the aromatic dicarboxylic acid imide include those represented by the general formula (6).

〔一般式（６）において、環Ａは置換基を有していてもよい芳香環を表し、Ｍ¹はアルカリ金属を表す。〕

In [Formula (6), ring A represents an aromatic ring which may have a substituent group, M ¹ is an alkali metal. ]

In the general formula (6), 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. 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. Examples of the alkali metal represented by M ¹ include lithium, sodium, potassium, rubidium, cesium, and francium.

  Examples of the alkali metal salt of the aromatic dicarboxylic acid imide include those represented by the general formulas (6-1) to (6-7).

〔一般式（６−１）〜（６−７）において、Ｍ¹はアルカリ金属を表す。〕

[In General Formulas (6-1) to (6-7), M ¹ represents an alkali metal. ]

  Examples of the alkali metal salt of aromatic sulfonic acid include those represented by the general formula (7).

〔一般式（７）において、Ａｒは置換基を有していてもよい芳香環を表し、Ｍ²はアルカリ金属を表す。〕

In [Formula (7), Ar represents an aromatic ring which may have a substituent, M ² represents an alkali metal. ]

In the general formula (7), the aromatic ring constituting Ar 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. 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. Examples of the alkali metal represented by M ² include lithium, sodium, potassium, rubidium, cesium, and francium.

  Examples of the alkali metal salt of aromatic sulfonic acid include those represented by general formulas (7-1) to (7-9).

〔一般式（７−１）〜（７−９）において、Ｍ²はアルカリ金属を表す。〕

[In General Formulas (7-1) to (7-9), M ² represents an alkali metal. ]

  Examples of the alkali metal salt of aromatic phosphonic acid include those represented by the general formula (8).

〔一般式（８）において、Ａｒは置換基を有していてもよい芳香環を表し、Ｍ³はアルカリ金属を表す。〕

In [Formula (8), Ar represents an aromatic ring which may have a substituent, M ³ represents an alkali metal. ]

In the general formula (8), the aromatic ring constituting Ar 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. 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. Examples of the alkali metal represented by M ³ include lithium, sodium, potassium, rubidium, cesium, and francium.

  Examples of the alkali metal salt of aromatic phosphonic acid include those represented by general formulas (8-1) to (8-7).

〔一般式（８−１）〜（８−７）において、Ｍ³はアルカリ金属を表す。〕

[In General Formulas (8-1) to (8-7), M ³ represents an alkali metal. ]

  Examples of the alkali metal salt of the aromatic carboxylic acid include those represented by the general formula (9).

〔一般式（９）において、Ａｒは置換基を有していてもよい芳香環を表し、Ｍ⁴はアルカリ金属を表す。〕

[In the general formula (9), Ar represents an aromatic ring which may have a substituent, and M ⁴ represents an alkali metal. ]

In the general formula (9), the aromatic ring constituting Ar 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. 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. Examples of the alkali metal represented by M ⁴ include lithium, sodium, potassium, rubidium, cesium, and francium.

  As an alkali metal salt of aromatic carboxylic acid, what is represented by general formula (9-1)-(9-9) is mentioned, for example.

  In the step (B), as a method of allowing the alkali metal salt to act on the block copolymer precursor, a method in which the alkali metal salt is added to a solution in which the block copolymer precursor is dissolved and stirred. Is mentioned.

  In the step (B), the alkali metal salt may be added to the reaction solution after the polymerization in the step (A). In addition, from the viewpoint of anion exchange efficiency, the precursor of the block copolymer is isolated from the polymerization solution after completion of the step (A), and the alkali metal salt is added to a solution obtained by dissolving the precursor in a new solvent. It is preferable.

  As a solvent capable of dissolving the block copolymer precursor, an aprotic solvent or a protic solvent can be used. Examples of aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform, Examples include carbon chloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluoromethylbenzene. Examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.

  In the step (B), the amount of the solvent used for dissolving the block copolymer precursor may be appropriately adjusted. For example, the amount is usually 2 ml to 10 ml with respect to 1 g of the block copolymer precursor. The range is preferably 2 ml to 5 ml.

  The amount of the at least one alkali metal salt selected from the group consisting of aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid in step (B) is a quaternary ammonium group. Is preferably 0.5 equivalents or more, more preferably 0.9 equivalents or more, preferably 1.1 equivalents or less, and more preferably 1.0 equivalents or less.

  In the step (B), the solution temperature when the block copolymer precursor is brought into contact with the alkali metal salt is usually 55 ° C to 70 ° C, preferably 55 ° C to 65 ° C, and the stirring time is usually 18 hours to 24 hours, preferably 20 hours to 22 hours.

  After completion of the reaction, the first composition containing the block copolymer is obtained by removing the solvent from the reaction solution. The obtained first composition is an impurity such as a precipitated salt (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as aromatic dicarboxylic imide). Is preferably removed by filtration.

(4.3 Step (C))
The method for producing the block copolymer preferably includes a step (C) of washing the block copolymer obtained in the step (B) with water. As the water washing method, a known washing method can be used, but liquid separation washing is preferable. Separation washing may be performed on the solution after completion of the step (B), or the first composition obtained by isolating the first composition of the block copolymer from the solution after completion of the step (B). You may perform with respect to the solution which melt | dissolved the composition in the appropriate solvent.

  As a specific example of the liquid separation washing, a solvent in which a block copolymer is dissolved and water are mixed, and then the separated aqueous layer is extracted. By washing with water, the content of the salt contained in the first composition (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide) is increased. It can be reduced more. Furthermore, repeated effects of separating and cleaning have a further effect. After the liquid separation washing, the second composition of the target block copolymer can be obtained by removing the solvent of the phase in which the block copolymer is dissolved under reduced pressure.

  The solvent for the above-described liquid separation operation may be any solvent that can dissolve the block copolymer and can be phase-separated from water. Examples thereof include ethyl acetate, butyl acetate, isopropyl acetate, and methyl isobutyl ketone. These may be used in combination. Moreover, the water used for washing may contain alcohol or the like.

  In the liquid separation washing, the amount of water used is preferably 0.1 to 10 times by volume, more preferably 0.5 times to the solvent phase in which the block copolymer is dissolved. ~ 5 times the amount. The liquid temperature at the time of liquid separation washing is preferably 10 ° C to 60 ° C, more preferably 30 ° C to 50 ° C, and particularly preferably 35 ° C to 45 ° C.

<5 Dispersant, pigment dispersion composition>
The dispersant of the present invention contains the block copolymer, the first composition or the second composition as a main component. In addition, it is preferable that the said dispersing agent consists only of the block copolymer of this invention, a 1st composition, or a 2nd composition. The pigment dispersion composition of the present invention contains the dispersant, a pigment, and a dispersion medium. In this case, the type and particle size of the pigment used are different depending on the application and are not particularly limited. The pigment dispersion composition can be used for a color filter. In the block copolymer characterizing the present invention, the tertiary amino group and quaternary ammonium base in the structure (B block) are strongly bonded to the acidic group of the pigment treated with the acidic pigment or the acidic group-containing dye derivative. The B block adsorbs to the pigment, or the aromatic part of the aromatic dicarboxylic acid imide anion which is a counter ion of the quaternary ammonium base adsorbs to the pigment skeleton part of the pigment, thereby improving the pigment dispersibility. It is thought to exert its effect. That is, since the dispersant of the present invention is a component that favorably disperses the pigment by this action, the type of pigment to be dispersed is not particularly limited.

  In the pigment dispersion composition, the content of the dispersant 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 pigment, and 10 parts by mass. More preferably, it is -50 mass parts.

  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 contained in the pigment dispersion composition, or a plurality of types may be used.

  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, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; 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, 188, 193, 194, 213; I. Orange pigments such as CI Pigment Orange 36, 38, 43; I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and the like; C.I. I. Green pigments such as Pigment Green 7, 36, 58; 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 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 and the like are preferable.

  The upper limit of the pigment content in the pigment dispersion composition is usually 80% by mass, preferably 70% by mass, and more preferably 60% by mass in the total solid content of the pigment dispersion composition. . Further, the lower limit of the pigment content in the pigment dispersion composition is usually 10% by mass, preferably 20% by mass, and preferably 30% by mass in the total solid content of the pigment dispersion composition. More preferred.

  As the dispersion medium, for example, a conventionally known 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 mono Ethyl 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, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monomethyl ether Glycol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and other glycol monoalkyl ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol Glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol Monoethyl 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 Glycol alkyl ether acetates such as diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate; Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, propyl ether, diethyl ether, dipropyl ether, Ethers such as diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, 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, methyl nonyl ketone, methoxymethyl pentano Ketones such as: ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol, etc. Monohydric or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; fats such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, Propyl acid, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxypropion Chain or cyclic esters such as methyl acrylate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Acetonitrile Nitriles such as benzonitrile and the like. The organic solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of pigments, solubility of the dispersant, applicability of the pigment dispersion composition, and the like. The solvent contained in the pigment dispersion composition may be only one type or a plurality of types.

  The content of the dispersion medium in the pigment dispersion composition is not particularly limited and can be appropriately adjusted. The upper limit of the content of the dispersion medium in the pigment dispersion composition is usually 99% by mass. The lower limit of the content of the dispersion medium in the pigment dispersion composition is usually 70% by mass and preferably 80% by mass in consideration of the viscosity suitable for application of the pigment dispersion composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the pigment dispersion composition.

  In the pigment dispersion composition of the present invention, an acidic group further having an acidic group is used in order to adsorb and adsorb the tertiary amino group and quaternary ammonium base in the block copolymer characterizing the present invention used as a dispersant. It is preferable to contain a pigment derivative of This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, the same or similar skeleton as the pigment constituting the pigment dispersion composition and the same or similar skeleton as the raw material of the pigment 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 carboxyl 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.

  The pigment dispersion composition of the present invention may contain a binder resin. The binder resin may be a polymer, for example. When the binder resin is a polymer, specific examples of monomers constituting the polymer include, for example, carboxyl groups such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, and maleic anhydride Containing unsaturated monomer: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) (Meth) acrylic such as 2-hydroxyethyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, cyclododecyl (meth) acrylate Acid ester; styrene, α-methylstyrene, 4-methylstyrene ( -Methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxystyrene), p-tert-butylstyrene, pn-butyl Examples thereof include aromatic unsaturated monomers (styrene monomers) such as styrene and p-tert-butoxystyrene.

  When the pigment dispersion composition is used as a colorant for a color filter, the binder resin is preferably a copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylic ester. Specific examples of such a copolymer include a copolymer of (meth) acrylic acid and butyl (meth) acrylate, a copolymer of (meth) acrylic acid and benzyl (meth) acrylate, And a copolymer of acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate. From the viewpoint of the affinity between the binder resin and the pigment, the binder resin is particularly preferably a copolymer of (meth) acrylic acid and benzyl (meth) acrylate. In the copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylic acid ester, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, and 10% by mass to all monomer components. It is preferable that it is 70 mass%, and it is more preferable that it is 20 mass%-70 mass%. Mw is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and even more preferably from 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength, etc. of the coating film formed from the pigment dispersion composition are good, and when the Mw is 100,000 or less, the aqueous alkaline solution of this coating film Developability due to is further improved.

  When the pigment dispersion composition is used as a colorant for a color filter, the acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, and more preferably 50 mgKOH / g to 150 mgKOH / g. 90 mg KOH / g to 150 mg KOH / g is more preferable. When the acid value of the binder resin is 20 mgKOH or more / g, the alkali developability when the pigment dispersion composition is used as a coating film is further improved, and when it is 170 mgKOH / g or less, the heat resistance is improved.

  The binder resin contained in the pigment dispersion composition may be only one type or a plurality of types. In the pigment dispersion 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 pigment. More preferably, it is 50 parts by mass.

  The pigment dispersion composition is obtained by mixing a pigment, a dispersant, a dispersion medium, a dye derivative, a binder resin and the like using a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader. The pigment dispersion composition is preferably filtered after mixing.

  The pigment dispersion composition may contain other additives as required. Examples of other additives include a photopolymerizable monomer, a photopolymerization initiator, a pH adjuster, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiseptic, and an antifungal agent. The photopolymerizable monomer is preferably a compound having at least two ethylenically unsaturated double bonds that are compatible with the binder resin. As such a compound, when the pigment dispersion composition is used as a colorant for a color filter, it has alkali solubility and has one or more acidic groups and two or more ethylenically unsaturated bonds in one molecule. A compound is preferable, and a compound having one or more acidic groups and three or more ethylenically unsaturated bonds in one molecule is more preferable. Examples of the compound having at least two ethylenically unsaturated double bonds include polyfunctional (meth) acrylates such as bifunctional (meth) acrylate and trifunctional or higher functional (meth) acrylate. Among these, trifunctional or higher functional (meth) acrylates are preferable. As a compound having one or more acidic groups and two or more ethylenically unsaturated bonds in one molecule, an acidic group-containing polyfunctional (meth) acrylate is more preferable, and a trifunctional or higher functional acid group-containing polyfunctionality. (Meth) acrylate is particularly preferred. The acidic group is not particularly limited as long as it can be alkali-developed, and examples thereof include a carboxy group, a sulfonic acid group, and a phosphoric acid group. The acidic group is preferably a carboxy group from the viewpoint of further improving the alkali developability and the handleability of the resin composition.

  A coating film of the pigment dispersion composition can be formed on the substrate by applying the pigment dispersion composition onto the substrate by a method such as spin coating, roll coating, or slit coating. After applying the pigment dispersion composition on the substrate, drying (desolvation treatment) or the like may be performed as necessary.

  When the pigment dispersion composition of the present invention is used as, for example, a patterning material for a color filter, the heat resistance of the block copolymer that characterizes the present invention used for the dispersant is excellent. It can be expected to suppress a decrease in contrast ratio and a change in hue.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these specific examples. Various physical properties were measured with the following equipment. 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)
HEMA: 2-hydroxyethyl methacrylate THFMAMA: tetrahydrofurfuryl methacrylate PCL5: 5-mol caprolactone adduct of 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Plaxel (registered trademark) FM5)
MAA: DMAEMA methacrylate: dimethylaminoethyl methacrylate BzCl: benzyl PIK: potassium phthalimide NaSS: p-sodium styrenesulfonate NaTS: sodium p-toluenesulfonate NaBA: sodium benzoate NaHPPA: monosodium phenylphosphonate PMA: propylene Glycol monomethyl ether acetate MP: 1-methoxy-2-propanol AcOEt: ethyl acetate

(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 as mobile phase, and differential refractive index detector as detector It was used. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 100 mg / mL, a sample injection amount of 10 μL, and a flow rate of 0.6 mL / min. A calibration curve (calibration curve) was prepared using polystyrene (manufactured by Tosoh Corporation, TSK Standard) as a standard substance, and a weight average molecular weight (Mw) and a number average molecular weight (Mn) were measured. Molecular weight distribution (PDI) 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 neutralized with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: 915 KF Ti-touch, manufactured by Metrohm). . 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 tetrahydrofuron, and the resulting solution was subjected to neutralization titration with a 0.5 mol / L potassium hydroxide / ethanol solution. The acid value (A) was calculated by the following formula.
A = 56.11 × Vs × 0.5 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.5 mol / L potassium hydroxide / ethanol solution required for titration (mL)
f: Potency of 0.5 mol / L potassium hydroxide / ethanol solution w: Mass (g) of measurement sample (converted to solid content)

(viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), using a cone rotor (1 ° 34 ′ × R24), the viscosity was measured at 25 ° C. and a rotor rotation speed of 100 rpm. .

(Heating weight reduction temperature)
It measured using the thermogravimetric / differential-heat simultaneous measuring apparatus (TG-DTA) (SII nanotechnology company make, TG-DTA6300). The measurement sample was dried under reduced pressure at 130 ° C. for 2 hours before measurement. The measurement conditions were a sample mass of about 10 mg, an air inflow rate of 200 ml / min, a heating rate of 10 ° C./min, and a measurement temperature range of 40 ° C. to 600 ° C. The temperature at which the sample mass decreased by 10% was read from the obtained TG curve, and this was taken as the heating weight decrease temperature.

(Halogen anion content)
Sample preparation was performed as follows. About 10 mg of the second composition substance was charged into a combustion furnace (trade name: AQF-2100H, manufactured by Mitsubishi Chemical Analytech). The heater of the combustion furnace was 900 ° C. (inside), the gas flow rate was 200 mL / min of argon, 400 mL / min of oxygen, 100 mL / min of argon for humidification, and the residence time of the combustion furnace was 15 minutes. The exhaust gas was captured by a collector (trade name: AU-250, manufactured by Mitsubishi Chemical Analytech). The sample solution was prepared by using ultrapure water as the absorbing solution and diluting 35 mL of the obtained water absorbing solution to 50 mL using ultrapure water.
The content of the halogen anion was measured using ion chromatography (trade name: DIONEX ICS-1600, manufactured by Thermo Scientific). The column used was Ion Pac AS-14A (manufactured by DIONEX), and the eluent used was an anion analysis eluent (trade name: AS12A, manufactured by DIONEX). The measurement conditions were a sample injection volume of 25 μL and a flow rate of 1.5 mL / min. A calibration curve (calibration curve) was prepared using a standard solution having a chlorine anion concentration of 1 ppm and 2 ppm as a standard substance, and the chlorine anion concentration was calculated.

<Manufacture of copolymer>
(Precursor No. 1 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%.

  To the reaction solution, a mixed solution of 54.3 g of DMAEMA previously substituted with argon, 0.41 g of AIBN and 36.2 g of PMA was added 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 benzyl chloride (15.3 g) was added to the diluted solution, followed by reaction at 60 ° C. for 10 hours for quaternization.

  After completion of the reaction, it was poured into stirred n-heptane. The precipitated polymer was filtered by suction and dried to obtain a precursor No. of block copolymer. 1 was obtained. Precursor No. of the obtained block copolymer 1 had an Mw of 7618, a PDI of 1.30, an acid value of 32 mgKOH / g, an amine value of 64 mgKOH / g, and a heating weight loss temperature of 254 ° C.

(Block copolymer precursor Nos. 2 to 12)
Block copolymer precursor no. The block copolymer precursor No. 1 was prepared in the same manner as in the preparation method of No. 1. 2 to 12 were produced. Tables 1 and 2 show the raw material monomers, organic tellurium compounds, organic ditellurium compounds, azo polymerization initiators, solvents, quaternizing agents, reaction conditions, and polymerization rates used. Tables 3 and 4 show the composition of precursors of each block copolymer, Mw, PDI, acid value, amine value, and heating weight reduction temperature.

(First composition No. 31 of block copolymer)
The block copolymer precursor No. obtained above. 1 PMA 110g and MP 110g were added to 87.5g and dissolved. Anion exchange was performed by adding 11.2 g of PIK to the obtained solution and reacting at 60 ° C. for 20 hours. After the reaction solution was filtered, the solvent was removed from the filtrate, and the first composition No. 1 of the block copolymer was removed. 31 was obtained. The obtained first composition No. No. 31 has a block copolymer Mw of 7479 and PDI of 1.23. The acid value of 31 was 31 mgKOH / g, the amine value was 101 mgKOH / g, and the heating weight loss temperature was 273 ° C.

(First composition No. 32-46 of block copolymer)
First composition No. of block copolymer In the same manner as the production method of No. 31, the first composition No. 32-46 were produced. Tables 5 and 6 show the raw material copolymers, anion exchangers, solvents and reaction conditions used. Tables 7 and 8 show the composition of the block copolymer contained in the first composition, Mw, PDI, and the acid value, amine value, and heating weight reduction temperature of the first composition.

(Block copolymer second composition No. 51)
The block copolymer precursor No. obtained above. 1 PMA 110g and MP 110g were added to 87.5g and dissolved. Anion exchange was performed by adding 11.2 g of PIK to the obtained solution and reacting at 60 ° C. for 20 hours. The obtained reaction solution was cooled, ethyl acetate and water were added, and the mixture was stirred at 40 ° C. for 1 hour. Liquid separation was performed to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure and dried to obtain a second composition No. 2 of the block copolymer. 51 was obtained. The second composition No. of the obtained block copolymer. 51, Mw of the block copolymer contained was 7852, and PDI was 1.21. Further, the acid value of the second composition was 32 mg KOH / g, the amine value was 89 mg KOH / g, the heating weight reduction temperature was 291 ° C., and the chlorine anion content was 3501 ppm (solid content conversion).

(Block copolymer second composition No. 52-65)
The second composition No. of the block copolymer. In the same manner as the production method of 51, the second composition No. 53-65 were produced. Tables 9 and 10 show the composition of the block copolymer contained in the second composition, Mw, PDI, and the acid value, amine value, and heating weight reduction temperature of the second composition. The obtained second composition No. The chlorine anion content of 59 was 6615 ppm (in terms of solid content).

<Production of pigment dispersion composition>
(Pigment dispersion composition 1)
C. I. Pigment Red254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) 10 parts by mass, precursor No. of block copolymer. 13 parts by mass, binder resin (polymerized at a mass ratio of benzyl methacrylate / methacrylic acid = 80/20, Mw = 1024, PDI = 1.83, acid value 130 mgKOH / g, PMA having a solid content of 39% by mass Solution) A blended composition was prepared by preparing 3 parts by mass, 3 parts by mass of MP, and 81 parts by mass of PMA, and stirring for 2 hours with a planetary ball mill (0.3 mm zirconia beads). The viscosity of the obtained pigment dispersion composition was 4.0 mPa · s.

(Pigment dispersion composition 2)
C. I. Pigment Red254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) 10 parts by mass, the second composition No. of the block copolymer. 51 3 parts by mass, binder resin (polymerized at a mass ratio of benzyl methacrylate / methacrylic acid = 80/20, Mw = 1024, PDI = 1.83, acid value 130 mgKOH / g, PMA having a solid content of 39% by mass Solution) A blended composition was prepared by preparing 3 parts by mass, 3 parts by mass of MP, and 81 parts by mass of PMA, and stirring for 2 hours with a planetary ball mill (0.3 mm zirconia beads). The viscosity of the obtained pigment dispersion composition was 3.0 mPa · s.

The present invention includes the following embodiments.
(Embodiment 1)
It has an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). A block copolymer characterized by

〔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^-は芳香族ジカルボン酸イミドアニオン、芳香族スルホン酸アニオン、芳香族ホスホン酸アニオンおよび芳香族カルボン酸アニオンよりなる群から選択される少なくとも１種を示す。〕

[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 at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion. ]

〔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 block copolymer according to embodiment 1, which is an AB type block copolymer.

(Embodiment 3)
The block copolymer of Embodiment 1 or 2 whose content rate of the structural unit derived from the vinyl monomer which has the said acidic group is 2 mass%-20 mass% in 100 mass% of said A blocks.

(Embodiment 4)
The block co-polymerization according to any one of embodiments 1 to 3, wherein the content of the structural unit represented by the general formula (1) is 30% by mass to 85% by mass in 100% by mass of the B block. Coalescence.

(Embodiment 5)
The block copolymer as described in any one of Embodiments 1-4 whose content rate of the said A block is 35 mass%-85 mass% in 100 mass% of block copolymers.

(Embodiment 6)
The 1st composition containing the block copolymer as described in any one of Embodiments 1-5.

(Embodiment 7)
The 1st composition of Embodiment 6 whose molecular weight distribution (PDI) of the said block copolymer is 2.0 or less.

(Embodiment 8)
A second composition obtained by washing the first composition of Embodiment 7 with water and drying.

(Embodiment 9)
A dispersant containing the block copolymer according to any one of Embodiments 1 to 5 , the first composition according to Embodiment 6 or 7 , or the second composition according to Embodiment 8.

(Embodiment 10)
A pigment dispersion composition comprising the dispersant according to embodiment 9, a pigment, and a dispersion medium.

(Embodiment 11)
The pigment dispersion composition according to embodiment 10, which is for a color filter.

(Embodiment 12)
A block having an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3) Preparing a copolymer precursor (A);
The precursor of the block copolymer obtained in the step (A) is at least one alkali selected from the group consisting of aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids. And a step (B) of obtaining a block copolymer by allowing a metal salt to act thereon.

〔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. ]

〔式（３）において、Ｒ³¹、Ｒ³²およびＲ³³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。Ｒ³¹、Ｒ³²およびＲ³³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。Ｘ³は２価の連結基を示す。Ｒ³⁴は水素原子またはメチル基を示す。Ｘ^-はハロゲンアニオンを示す。〕

[In the formula (3), R ³¹ , R ³² and R ³³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁻ represents a halogen anion. ]

(Embodiment 13)
The method for producing a block copolymer according to embodiment 12, wherein in the step (A), a precursor of the first block copolymer is prepared using living radical polymerization.

(Embodiment 14)
The manufacturing method of the block copolymer of Embodiment 12 or 13 provided with the process (C) which wash | cleans the block copolymer obtained at the said process (B) with water.

  In the block copolymer of the present invention, alkali development is facilitated because the A block has an acidic group. Moreover, since the counter ion of the quaternary ammonium cation of the B block is an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, or an aromatic carboxylic acid anion, the heat resistance is excellent. Therefore, the block copolymer of this invention can be used conveniently for the pigment dispersion composition for color filters used for manufacture of the color filter which employ | adopted alkali image development.

Claims (14)

It has an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). A block copolymer characterized by

[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 at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion. ]

[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. ]   2. The block copolymer according to claim 1, which is an AB type block copolymer.   The block copolymer according to claim 1 or 2, wherein a content of a structural unit derived from the vinyl monomer having an acidic group is 2% by mass to 20% by mass in 100% by mass of the A block.   The content of the structural unit represented by the general formula (1) is 30% by mass to 85% by mass in 100% by mass of the B block. Coalescence.   The block copolymer as described in any one of Claims 1-4 whose content rate of the said A block is 35 mass%-85 mass% in 100 mass% of block copolymers.   The 1st composition containing the block copolymer as described in any one of Claims 1-5.   The first composition according to claim 6, wherein the block copolymer has a molecular weight distribution (PDI) of 2.0 or less.   The 2nd composition obtained by washing with water and drying the 1st composition of Claim 7. The dispersing agent containing the block copolymer as described in any one of Claims 1-5 , the 1st composition as described in Claim 6 or 7 , or the 2nd composition as described in Claim 8.   A pigment dispersion composition comprising the dispersant according to claim 9, a pigment, and a dispersion medium.   The pigment dispersion composition according to claim 10, which is used for a color filter. A block having an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3) Preparing a copolymer precursor (A);
The precursor of the block copolymer obtained in the step (A) is at least one alkali selected from the group consisting of aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids. And a step (B) of obtaining a block copolymer by allowing a metal salt to act thereon.

[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 the formula (3), R ³¹ , R ³² and R ³³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁻ represents a halogen anion. ]   The method for producing a block copolymer according to claim 12, wherein in the step (A), a precursor of the block copolymer is prepared using living radical polymerization. The method for producing a block copolymer according to claim 12 or 13, comprising a step (C) of washing the block copolymer obtained in the step (B) with water.