JP6640436B2 - Block copolymer, dispersant, coloring composition and color filter - Google Patents

Description

  The present invention relates to a block copolymer, a dispersant, a coloring composition, and a color filter.

  A coloring composition obtained by mixing a coloring material (a pigment, a dye, etc.), a dispersing agent, and a dispersion medium (a solvent) and dispersing the coloring material is used in a wide range of fields such as a color filter of a liquid crystal display. . For example, in a color filter, in order to apply a coloring material to a substrate, a coating film made of a coloring composition is formed on the substrate, exposed to light through a photomask having a desired pattern shape, and alkali development is performed. .

  In the production of liquid crystal displays, after forming a pattern shape of a coloring material, a transparent electrode for driving the liquid crystal is formed thereon by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, their formation is generally performed at a high temperature of 200 ° C. or higher.

  On the other hand, the coloring composition is required to be excellent in various properties such as sharpness and high transparency, and fine particles of the coloring material are being used. When the coloring material becomes fine particles, the surface energy is increased to cause aggregation of the coloring material, storage stability is poor, and the viscosity of the coloring composition is increased. Therefore, a resin-type dispersant is used. However, when a large amount of resin-type dispersant is used, there is a problem in heat resistance such as a decrease in contrast ratio of a color filter and a change in hue before and after a step involving high heat. In Patent Document 1, therefore, in order to obtain a colored composition having both heat resistance and dispersibility, it is composed of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. It has been proposed to use an AB block copolymer as a dispersant (see Patent Document 1 (Claim 1, paragraphs 0049 to 0058)).

JP 2012-068559 A

  Conventionally, a coloring composition with improved heat resistance has been proposed, but a method for improving the heat resistance of the resin-type dispersant itself has not been proposed. The present invention has been made in view of the above circumstances, and has as its object to provide a block copolymer which can be used, for example, as a dispersant and has excellent heat resistance.

  The block copolymer of the present invention that can solve the above problems has an A block and a B block, and the A block includes a structural unit derived from a (meth) acrylic vinyl monomer, and The content of the structural unit represented by the following general formula (1) in the A block is less than 5% by mass, and the content of the structural unit represented by the following general formula (1) in the B block is 5% by mass. % Or more.

〔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。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２−１）または一般式（２−２）で表される対イオンを示す。
式（２−１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２−２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. R ¹⁵ represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by the general formula (2-1) or (2-2).
In the formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In the formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

  The block copolymer of the present invention has an A block having a low content of the structural unit represented by the general formula (1) and a B block having a high content of the structural unit represented by the general formula (1). . By having these A blocks and B blocks, the block copolymer of the present invention has excellent dispersibility. Further, in the block copolymer of the present invention, the counter ion of the quaternary ammonium base contained in the structural unit represented by the general formula (1) is a sulfate ion or a sulfonate ion. Therefore, the block copolymer of the present invention has excellent heat resistance.

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

  The block copolymer of the present invention has an A block and a B block, wherein the A block contains a structural unit derived from a (meth) acrylic vinyl monomer, and the following general formula (1) ) Is less than 5% by mass, and the content of the structural unit represented by the following general formula (1) in the B block is 5% by mass or more. .

〔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。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２−１）または一般式（２−２）で表される対イオンを示す。
式（２−１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２−２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. R ¹⁵ represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by the general formula (2-1) or (2-2).
In the formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In the formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

  Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

<Block copolymer>
The block copolymer of the present invention contains an A block and a B block.

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

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

(A block)
The A block is a polymer block containing a structural unit derived from a (meth) acrylic vinyl monomer. The structural unit derived from the (meth) acrylic vinyl monomer in the A block may be only one type, or may have two or more types. By using a structural unit derived from a (meth) acrylic vinyl monomer, the heat resistance of the block copolymer can be increased while maintaining high affinity with a solvent and a binder resin.

  The content of the structural unit derived from the (meth) acrylic vinyl monomer is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, in 100% by mass of the A block. Particularly preferably, it is 100% by mass.

  The (meth) acrylic vinyl monomer includes a (meth) acrylate having a chain alkyl group (straight chain alkyl group or branched chain alkyl group), a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having an aromatic group. Acrylate, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, (meth) acrylate having an alkoxy group, and having an oxygen-containing heterocyclic group Examples thereof include (meth) acrylate, (meth) acrylate having an acidic group, and (meth) acrylic acid, and one or more of these can be used in combination.

  As the (meth) acrylate having a straight-chain alkyl group, a (meth) acrylate having a straight-chain alkyl group having 1 to 20 carbon atoms in a straight-chain alkyl group is preferable, and the straight-chain alkyl group having 1 to 20 carbon atoms. A (meth) acrylate having a linear alkyl group of 10 is more preferred. Examples of the (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, Examples include n-octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, n-lauryl (meth) acrylate, and n-stearyl (meth) acrylate.

  As the (meth) acrylate having a branched alkyl group, a (meth) acrylate having a branched alkyl group having 1 to 20 carbon atoms in the branched alkyl group is preferable, and the carbon number of the branched alkyl group is preferably 1 to 20. A (meth) acrylate having a branched alkyl group of 10 is preferred. Examples of the (meth) acrylate having a branched alkyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, Examples include ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and isodecyl (meth) acrylate.

  The (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include a cyclic alkyl group having a single ring structure (eg, a cycloalkyl group) and a cyclic alkyl group having a bridged ring structure (eg, an adamantyl group, a norbornyl group, and an isobornyl group). Specific examples of (meth) acrylates having a monocyclic cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. Specific examples of the (meth) acrylate having a cyclic alkyl group having a bridged ring structure include isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and 2-adamantyl (meth) acrylate. Can be

  The (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms. Examples of the aromatic group include an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group, and the like, particularly, a phenyl group, a benzyl group, a tolyl group, and a phenoxyethyl group. Groups are preferred. Specific examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

  Examples of the (meth) acrylate having a polyalkylene glycol structural unit include polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth) acrylate, and polyethylene. (Meth) acrylate having a polyethylene glycol structural unit such as glycol (degree of polymerization = 2 to 10) propyl ether (meth) acrylate; polypropylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2 to 10) (meth) a having a polypropylene glycol structural unit such as ethyl ether (meth) acrylate and polypropylene glycol (degree of polymerization = 2 to 10) propyl ether (meth) acrylate Relate; and the like.

  Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Examples include hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate.

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

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

  The (meth) acrylate having an oxygen-containing heterocyclic group is preferably a (meth) acrylate having a 4- to 6-membered oxygen-containing heterocyclic group. Specific examples of the (meth) acrylate having an oxygen-containing heterocyclic group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, and (2- Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropaneformal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate and the like.

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 ). Examples of the (meth) acrylate having an acidic group include a (meth) acrylate having a carboxy group such as a monomer obtained by reacting a hydroxyalkyl (meth) acrylate with an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride. A (meth) acrylate having a sulfonic acid group such as ethyl sulfonate (meth) acrylate; a (meth) acrylate having a phosphoric acid group such as 2- (phosphonooxy) ethyl (meth) acrylate; Is a (meth) acrylate having a carboxy group.

  The (meth) acrylic vinyl monomer preferably contains (meth) acrylate having a polyalkylene glycol structural unit and / or (meth) acrylate having a lactone-modified hydroxy group. When using these monomers, the total content of the structural units derived from the (meth) acrylate having a polyalkylene glycol structural unit and the (meth) acrylate having a lactone-modified hydroxy group in the A block is as follows: In the A block 100 mass%, 5 mass% or more is preferable, 10 mass% or more is more preferable, 20 mass% or more is more preferable, 80 mass% or less is preferable, and 70 mass% or less is more preferable. , More preferably 60% by mass or less, particularly preferably 50% by mass or less.

  It is also preferable to use only one of these (meth) acrylates having a polyalkylene glycol structural unit and / or (meth) acrylate having a lactone-modified hydroxy group.

  As one embodiment of the (meth) acrylic vinyl monomer, the (meth) acrylic vinyl monomer includes a (meth) acrylate having a chain alkyl group (linear alkyl group or branched alkyl group) and a cyclic alkyl group. (Meth) acrylate having (meth) acrylate having aromatic group, (meth) acrylate having hydroxy group, (meth) acrylate having alkoxy group, (meth) acrylate having oxygen-containing heterocyclic group, having acidic group It is preferable to contain only one or more selected from (meth) acrylate and (meth) acrylic acid, and only a (meth) acrylate having a polyalkylene glycol structural unit. By using these (meth) acrylic vinyl monomers, dispersibility and dispersion stability can be further improved. In this case, the content of the structural unit derived from the (meth) acrylate having a polyalkylene glycol structural unit is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 100% by mass of the A block. Is 20% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less.

  As another embodiment of the (meth) acrylic vinyl monomer, the (meth) acrylic vinyl monomer may be a (meth) acrylate having a chain alkyl group (a straight chain alkyl group or a branched chain alkyl group), or a cyclic alkyl group. (Meth) acrylate having an aromatic group, (meth) acrylate having an aromatic group, (meth) acrylate having a hydroxy group, (meth) acrylate having an alkoxy group, (meth) acrylate having an oxygen-containing heterocyclic group, and an acidic group. It is preferable to use only one (meth) acrylate having at least one selected from (meth) acrylate and (meth) acrylic acid and a (meth) acrylate having a lactone-modified hydroxy group. By using these (meth) acrylic vinyl monomers, dispersibility, heat resistance and alkali developability can be improved. In this case, the content of the structural unit derived from the (meth) acrylate having a lactone-modified hydroxy group is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 100% by mass of the A block. It is 20% by mass or more, particularly preferably 30% by mass or more, most preferably 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.

  Examples of the structural unit derived from the (meth) acrylate having the polyalkylene glycol structural unit include a structural unit represented by the following general formula (7).

〔一般式（７）において、ｎ７は２〜１５０の整数を表す。Ｒ⁷¹は水素原子又は炭素数が１〜６のアルキル基を表す。Ｒ⁷²は炭素数が１〜６のアルキレン基を表す。Ｒ⁷³は水素原子またはメチル基を表す。〕

[In the general formula (7), n7 represents an integer of 2 to 150. R ⁷¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁷² represents an alkylene group having 1 to 6 carbon atoms. R ⁷³ represents a hydrogen atom or a methyl group. ]

N7 in the formula (7) is preferably an integer of 2 to 50, more preferably an integer of 2 to 10.
The alkyl group having 1 to 6 carbon atoms represented by R ⁷¹ may be linear or branched, but is preferably linear. Specific examples of the alkyl group of carbon number 1 to 6 represented by R ⁷¹ include methyl group, ethyl group, n- propyl group, n- butyl group, a pentyl group, a hexyl group. R ⁷¹ is preferably an alkyl group having 1 to 3 carbon atoms.
The alkylene group having 1 to 6 carbon atoms represented by R ⁷² may be linear or branched, but is preferably linear. Specific examples of the above alkylene group having a carbon number represented by R ⁷² is 1-6, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like. R ⁷² is preferably an alkylene group having 2 to 4 carbon atoms.

  Examples of the structural unit derived from the (meth) acrylate having a lactone-modified hydroxy group include a structural unit represented by the following general formula (8).

〔一般式（８）において、ｎ８は１〜１０の整数を表す。Ｒ⁸¹は炭素数が１〜１０のアルキレン基を表す。Ｒ⁸²は炭素数が１〜１０のアルキレン基を表す。Ｒ⁸³は水素原子またはメチル基を表す。〕

[In the general formula (8), n8 represents an integer of 1 to 10. R ⁸¹ represents an alkylene group having 1 to 10 carbon atoms. R ⁸² represents an alkylene group having 1 to 10 carbon atoms. R ⁸³ represents a hydrogen atom or a methyl group. ]

N8 in the above formula (8) is preferably an integer of 1 to 7, more preferably an integer of 1 to 5.
The alkylene group having 1 to 10 carbon atoms represented by R ⁸¹ may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁸¹ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, Examples include a nonamethylene group and a decamethylene group. R ⁸¹ is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms.
The alkylene group having 1 to 10 carbon atoms represented by R ⁸² may be linear or branched, but is preferably linear. Specific examples of the above alkylene group having a carbon number represented by R ⁸² is 1-10, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Examples include a nonamethylene group, a decamethylene group, and a 1-methylethylene group. R ⁸² is preferably an alkylene group having 1 to 5 carbon atoms.

  The A block has a content of a structural unit represented by the following general formula (1) of less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less. More preferably, it does not contain the represented structural unit. As the content of the structural unit represented by the general formula (1) in the A block is lower, the dispersibility of the coloring material is improved.

  The A block may have a structural unit other than the structural unit derived from the (meth) acrylic vinyl monomer. Other structural units that can be included in the A block are not particularly limited as long as they are formed by a vinyl monomer that can be copolymerized with both a (meth) acrylic vinyl monomer and a vinyl monomer that forms a B block described below. Absent. Vinyl monomers capable of forming other structural units of the A block may be used alone or in combination of two or more.

  Specific examples of the vinyl monomer capable of forming another structural unit of the A block include an α-olefin, an aromatic vinyl monomer, a vinyl monomer containing a hetero ring, vinyl amide, vinyl carboxylate, and dienes. 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 hetero ring include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine and the like.
Examples of vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam, and the like.
Examples of the 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.

  The A block has a structural unit derived from a vinyl monomer having an acidic group (preferably, (meth) acrylate or (meth) acrylic acid having an acidic group), so that the solubility in an alkali developing solution is increased, and the alkali developing property is increased. Can be improved. However, when the ratio increases, the affinity with the solvent and the alkali-soluble resin may be reduced. Therefore, it is preferable that the ratio of the structural unit derived from the vinyl monomer having an acidic group be a ratio at which the overall acid value of the block copolymer is lower than the amine value.

  When a structural unit derived from a vinyl monomer having an acidic group is contained, the content is preferably 2% by mass or more, and more preferably 20% by mass or less in 100% by mass of the A block. When the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate upon neutralization with an alkali increases in alkali development, and when the content is 20% by mass or less, the hydrophilicity is high. This makes it possible to prevent the formed pixels from being cluttered.

  The A block preferably 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 group is present in the A block, when used as a dispersant, the coloring material is adsorbed on both the A block and the B block, and the dispersing performance of the coloring material is reduced. The content of the structural unit derived from the vinyl monomer having an amino group in the A block (including those having a quaternized amino group) is preferably 2% by mass or less, more preferably 1% by mass or less, The content is more preferably 0.1% by mass or less, and most preferably 0% by mass.

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

(B block)
The B block is a polymer block containing a B block containing a structural unit represented by the following general formula (1).

[Structural unit represented by general formula (1)]
The structural unit represented by the general formula (1) may be only one type, or may have two or more types. By using the structural unit represented by the general formula (1), the adsorptivity to the coloring material is high, and the heat resistance can be increased.

〔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。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２−１）または一般式（２−２）で表される対イオンを示す。
式（２−１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２−２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. R ¹⁵ represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by the general formula (2-1) or (2-2).
In the formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In the formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

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

As the group represented by R ^{11 to} R ¹³ , 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 are preferable. , a methyl group, an ethyl group, a propyl group, a benzyl group (-CH ₂ C ₆ H ₅₎ is more preferable.

Examples of the cyclic structure formed by bonding two or more of R ^{11 to} R ¹³ to each other include, for example, a 5- to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of them. Can be The nitrogen-containing hetero ring preferably has no aromaticity, and is 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、Ｒ¹⁶は、Ｒ¹¹〜Ｒ¹³のいずれかである。Ｒ¹⁷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Ｒ¹⁷は、それぞれ同一でも異なっていてもよい。〕

[In the general formulas (11-1), (11-2) and (11-3), R ¹⁶ is any one of R ^{11 to} R ¹³ . R ¹⁷ 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 the integer of 0-4. When 1 is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ¹⁷ may be the same or different. ]

Group represented by R ¹⁴ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and the like.

Examples of the alkyl group represented by R ²¹ and R ²² include a straight-chain alkyl group, a branched-chain alkyl group, and a cyclic alkyl group. A straight-chain alkyl group having 1 to 20 carbon atoms is more preferable. Is a linear alkyl group having 1 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

Examples of the aromatic group represented by R ²¹ and R ²² include an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group, and the like. ~ 12 aromatic groups are preferred. Specific examples include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthalene group.

  Examples of the sulfate ion represented by the formula (2-1) include alkyl sulfate ions such as methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion and butyl sulfate ion; and aromatic acids such as phenyl sulfate ion, benzyl sulfate ion and tolyl sulfate ion. Group sulfate ion; and the like.

  Examples of the sulfonic acid ion represented by the formula (2-2) include alkylsulfonic acid ions such as methanesulfonic acid ion, ethanesulfonic acid ion, propanesulfonic acid ion, and butanesulfonic acid ion; benzenesulfonic acid ion, toluenesulfonic acid Ion, aromatic sulfonic acid ion such as phenylmethanesulfonic acid; and the like.

  Specific examples of the vinyl monomer capable of forming the structural unit represented by the general formula (1) include (meth) acryloyloxyethyltrimethylammonium methyl sulfate, (meth) acryloyloxypropyltrimethylammonium methyl sulfate, ( (Meth) acryloyloxybutyltrimethylammonium methylsulfate, (meth) acryloyloxyethyldimethylethylammonium ethylsulfate, (meth) acryloyloxypropyldimethylethylammonium ethylsulfate, (meth) acryloyloxybutyldimethylethylammonium Ethyl sulfate, (meth) acryloyloxyethyltrimethylammonium toluene-4-sulfonate, (meth) acryloyloxypropyl Ammonium toluene-4-sulfonate, and (meth) acryloyloxy-butyl trimethyl ammonium toluene-4-sulfonate and the like.

  The content of the structural unit represented by the general formula (1) is preferably 5% by mass or more, 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more in 100% by mass of the B block. And preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, particularly preferably 70% by mass or less. By setting the content of the structural unit represented by the general formula (1) in this range, it is considered that the colorant has high affinity.

When R ²¹ and R ²² are alkyl groups, the content of the structural unit represented by the general formula (1) is preferably 30% by mass or more, more preferably 35% by mass, in 100% by mass of the B block. As described above, the content is more preferably 40% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

When R ²¹ and R ²² are aromatic groups, the content of the structural unit represented by the general formula (1) is preferably 33% by mass or more, more preferably 38% by mass, in 100% by mass of the B block. % Or more, more preferably 43% by mass or more, preferably 85% by mass or less, more preferably 75% by mass or less, and still more preferably 65% by mass or less.

[Structural unit represented by general formula (3)]
The B block may contain a structural unit represented by the following general formula (3).

〔式（３）において、Ｒ³¹およびＲ³²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およびＲ³²は互いに結合して環状構造を形成していてもよい。Ｒ³³は、鎖状の２価の炭化水素基を示す。Ｒ³⁴は、水素原子またはメチル基を示す。〕

[In the formula (3), R ³¹ and R ³² each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a chain divalent hydrocarbon group. R ³⁴ represents a hydrogen atom or a methyl group. ]

The chain hydrocarbon group represented by R ³¹ or R ³² includes both linear and branched chains. Examples of the substituent of the chain hydrocarbon group represented by R ³¹ or R ³² include an alkoxy group, a benzoyl group, and a hydroxy group. Examples of the substituent of the cyclic hydrocarbon group represented by R ³¹ or R ³² include a chain alkyl group, an alkoxy group, and a hydroxy group.

Examples of the group represented by R ³¹ or R ³² 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. Preferably, 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 ³¹ or R ³² with each other include a 5- to 7-membered nitrogen-containing heterocycle or a condensed ring formed by condensing two of them. The nitrogen-containing hetero ring preferably has no aromaticity, and is 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、Ｒ³⁵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Ｒ³⁵は、それぞれ同一でも異なっていてもよい。〕

[In the general formulas (31-1), (31-2), and (31-3), R ³⁵ 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 the integer of 0-4. When 1 is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ³⁵ may be the same or different. ]

Group represented by R ³³ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms. Specific examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and the like.

  The content of the structural unit represented by the general formula (3) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass in 100% by mass of the B block. It is preferably at least 95% by mass, more preferably at most 70% by mass, still more preferably at most 65% by mass, particularly preferably at most 40% by mass. By setting the content of the structural unit represented by the general formula (3) in this range, it is considered that the colorant has high affinity.

  The B block may include only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3), or may include another structural unit. From the viewpoint of maintaining affinity with the coloring material, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) in the B block is 80% by mass or more. Is preferably 90% by mass or more, more preferably 95% by mass or more. The mass ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (3) in the B block (the structural unit represented by the formula (1) / the structural unit represented by the formula (3)) 30/70 or more, more preferably 35/65 or more, still more preferably 40/60 or more, preferably 90/10 or less, more preferably 85/15 or less, and still more preferably 80/20 or less.

  Further, the B block preferably does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 5% by mass or less, more preferably 2% by mass or less, and still more preferably 1% 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 vinyl monomers exemplified as specific examples of the vinyl monomer capable of forming the other structural unit of the A block.

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

(Block copolymer)
The structure of the block copolymer of the present invention is preferably a linear block copolymer. Further, the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, A block is A and 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 preferable that the copolymer has at least one structure selected from the group consisting of: Among these, from the viewpoints of handleability during processing and physical properties of the composition, an AB diblock copolymer or an ABA triblock copolymer is preferable, and heat resistance and alkali development From the viewpoint of properties, AB type diblock copolymers are more preferable. In the case of an ABA triblock copolymer, two A blocks located at both ends may be the same or different.

  The content of the A block is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, and preferably 95% by mass or less, based on 100% by mass of the whole block copolymer. The content is more preferably 90% by mass or less, and further preferably 80% by mass or less. The content of the B block is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 50% by mass or less, based on 100% by mass of the whole block copolymer. It is more preferably at most 45% by mass, further preferably at most 40% by mass. By adjusting the content of the A block and the B block within the above range, both heat resistance and dispersion performance when used as a dispersant can be achieved in a well-balanced manner.

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

  When the block copolymer has A1 blocks and A2 blocks as A blocks, the mass ratio (A1 / A2) of these blocks is preferably 0.4 or more, more preferably 0.7 or more, and still more preferably 0.8. 2.3 or less, more preferably 1.5 or less, and even more preferably 1.2 or less.

  The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter, referred to as “GPC”). The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 6,000 or more. It is preferably at most 000, more preferably at most 30,000, further preferably at most 25,000, particularly preferably at most 20,000. When the weight average molecular weight is within the above range, the dispersing performance when used as a dispersant becomes better.

  The molecular weight distribution (PDI) of the block copolymer is preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight of block copolymer (Mw)) / (number average molecular weight of block copolymer (Mn)). The smaller the PDI, the narrower the width of the molecular weight distribution, and the resulting copolymer becomes uniform in molecular weight. When the value is 1.0, the width of the molecular weight distribution is the narrowest. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.2, those having a small molecular weight and those having a large molecular weight are included.

  The amine value of the block copolymer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further more preferably 30 mgKOH / g or more, from the viewpoints of adsorbability to the colorant and dispersibility of the colorant. It is preferably at most 200 mgKOH / g, more preferably at most 150 mgKOH / g, even more preferably at most 100 mgKOH / g.

  When the block copolymer contains a structural unit having an acidic group, the acid value of the block copolymer is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and still more preferably 15 mgKOH / g or more. , 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, and even more preferably 35 mgKOH / g or less. By setting the acid value within this range, the block copolymer can suitably act on the binder resin (alkali-soluble resin) without impairing the affinity for the colorant.

  The content of the halogen anion in the block copolymer is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 2.5 ppm or less, and particularly preferably 0 ppm. The lower the halogen anion content of the block copolymer, the higher the heat resistance of the block copolymer.

(Method for producing block copolymer)
As a method for producing the block copolymer, a method in which an A block is first produced by a polymerization reaction of a vinyl monomer, and a monomer of a B block is polymerized in an A block; A method of polymerizing the monomer of the block; a method of separately producing the A block and the B block, and a method of coupling the A block and the B block; a method of producing the A block first, and expressing the B block by the formula (3). A monomer composition containing a vinyl monomer capable of forming the structural unit to be formed is polymerized, and a part of the tertiary amine structure of the structural unit represented by the formula (3) in the obtained polymer is quaternized. Method: A monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (3) is polymerized, and a monomer of the A block is polymerized on the polymerized product. A) quaternizing a part of the tertiary amine structure of the structural unit represented by the formula: A block and a block having the structural unit represented by the formula (3) are separately produced, and these blocks are separated by a cup. After ringing, a method of quaternizing some tertiary amine structures of the structural unit represented by the formula (3) in the obtained polymer.

  The block copolymer of the present invention is obtained by quaternizing a block copolymer having a structural unit represented by the formula (3) with an alkyl halide or the like, and then converting the halogen anion into a sulfate ion and / or a sulfonate ion. It can also be obtained by exchanging. However, in such a method, halogen tends to remain as an impurity in the obtained block copolymer. Therefore, the block copolymer of the present invention is a block copolymer having a first block and a second block, wherein the first block contains a structural unit derived from a (meth) acrylic vinyl monomer, and The content of the structural unit represented by the general formula (3) in the first block is less than 5% by mass, and the content of the structural unit represented by the general formula (3) in the second block is 5% by mass. After synthesizing a block copolymer of not less than mass%, at least a part of the tertiary amine structure of the structural unit represented by the formula (3) in the obtained block copolymer is a sulfate compound and / or Those obtained by quaternization with a sulfonic acid compound are preferred. By using a sulfuric acid compound and / or a sulfonic acid compound as the quaternizing agent, a block copolymer containing no halogen can be obtained.

  The polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the block copolymer is preferably a polymer obtained by living radical polymerization. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the termination reaction and the chain transfer reaction cause the deactivation of the growth terminal, which tends to easily produce a mixture of polymers having various molecular weights and heterogeneous compositions. In contrast, the living radical polymerization method, while maintaining the simplicity and versatility of the conventional radical polymerization method, is unlikely to cause a termination reaction or chain transfer and grows without deactivating the growth terminal, so that the molecular weight distribution This is preferred because it is easy to produce a polymer having a precise composition and 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 such as a method used (TERP method). Since the ATRP method uses an amine-based complex, it cannot be used without protecting the acidic group of the vinyl monomer having an acidic group. In the RAFT method, when various types of monomers are used, a low molecular weight distribution is unlikely to occur, and there may be a problem such as a sulfur odor or coloring. Among these methods, it is preferable to use the TERP method from the viewpoints of diversity of usable monomers, control of molecular weight in a polymer region, uniform composition, and coloring.

  The TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. For example, WO2004 / 14848, WO2004 / 14962, WO No. 2004/072126 and WO 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) A vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (4).
(B) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (4) and an azo-based polymerization initiator.
(C) A vinyl monomer is polymerized using a mixture of an organic telluride compound represented by the general formula (4) and an organic ditelluride compound represented by the general formula (5).
(D) A vinyl monomer is polymerized using a mixture of an organic telluride compound represented by the general formula (4), an azo-based polymerization initiator, and an organic ditelluride 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。
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 the general formula (4), R ⁴¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. 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, an aryl group having 1 to 8 carbon atoms, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In the general formula (5), R ⁴¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group. ]

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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. And a straight-chain or branched-chain alkyl group such as an octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, and more preferably 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.

Groups represented by R ⁴² and R ⁴³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each group is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. And a straight-chain or branched-chain alkyl group such as an octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

Group represented by R ⁴⁴ is an alkyl group, an aryl group having 1 to 8 carbon atoms, 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 It is a propargyl group, which is specifically as follows.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. And a linear or branched alkyl group such as a octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
Examples of the aryl group include a phenyl group and a naphthyl group. Preferably it is a phenyl group.
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 ⁴¹¹ (where R ⁴¹¹ is a carbon atom). An alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group having 1 to 8 carbon atoms or an aryloxy group), a sulfonyl group, and a trifluoromethyl group. Further, these substituents are preferably substituted one or two times.
Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
As the alkoxy group, a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom is preferable. For example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert- Butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.
Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
Examples of the amide group include -CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group).
As the oxycarbonyl group, a group represented by -COOR ⁴³¹ (R ⁴³¹ is a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms) is preferable, and examples thereof include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl. Group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyloxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include a methoxycarbonyl group and an ethoxycarbonyl group.
As the allyl group, -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ = CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ represent Each independently represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and the respective substituents may be connected by a cyclic structure).
Examples of the propargyl group include -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴⁵³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. , An aryl group or a silyl group).

  Specific examples of the organic tellurium compound represented by the general formula (4) include (methylteranylmethyl) benzene, (methylteranylmethyl) naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, and ethyl-2-yl. Methyl-2-n-butylteranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylterranyl-propionate or (3-trimethylsilylpropargyl) ) -2-Methyl-2-methylteranyl-propionate and the like organic compounds described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870. All of tellurium compounds Can Shimesuru.

  Specific examples of the organic ditelluride compound represented by the general formula (5) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, and dicyclopropyl ditelluride. -N-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis Examples include-(p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, dipyridyl ditelluride, and the like.

  The azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in ordinary 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-methylbutylamide), 2,2′-azobis (4-methoxy-2,4 -Dimethylvaleronitrile) (V-70), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Lopan], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Examples include azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), and 2,2′-azobis (N-cyclohexyl-2-methylpropionamide).

  In the polymerization step, the vinyl monomer and the organic tellurium compound of the general formula (4) are further added to the vinyl monomer and the organic tellurium compound according to the type of the vinyl monomer in order to promote the reaction, control the molecular weight and the molecular weight distribution, etc. An azo polymerization initiator and / or an organic ditelluride compound of the general formula (5) are mixed. At this time, examples of the inert gas include nitrogen, argon, and helium. Preferably, argon and nitrogen are good.

  The amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted depending on the physical properties of the desired copolymer. It is preferable that the vinyl monomer is 5 mol to 10000 mol per 1 mol of the organic tellurium compound of the general formula (4).

  When the organic tellurium compound of the general formula (4) and the azo-based polymerization initiator (b) are used in combination, the azo-based polymerization initiator is used in an amount of 0.01 mol to 10 mol per 1 mol of the organic tellurium compound of the general formula (4). It is preferable that

  When the organic telluride compound of the general formula (4) and the organic ditelluride compound of the general formula (5) are used in combination, 1 mol of the organic tellurium compound of the general formula (4) is used for 1 mol of the organic tellurium compound of the general formula (4). It is preferable that the ditellurium compound be 0.01 mol to 100 mol.

  When the organic telluride compound represented by the general formula (4), the organic ditelluride compound represented by the general formula (5) and the azo-based polymerization initiator are used in combination, 1 mol of the organic tellurium compound represented by the general formula (4) may be used. The amount of the organic ditelluride compound of the formula (5) is preferably 0.01 mol to 100 mol, and the amount of the azo-based polymerization initiator is preferably 0.01 mol to 10 mol per 1 mol of the organic telluride compound of the general formula (4).

  The polymerization reaction can be carried out without a solvent, but may be carried out by using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture. Examples of usable aprotic solvents include, for example, anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, and chloroform. , Carbon tetrachloride, 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 to be used may be appropriately adjusted. For example, the amount 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, per 1 g of the vinyl monomer. It is preferably 10 ml or less, more preferably 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 obtained copolymer, and usually, the mixture is stirred at 0 ° C to 150 ° C for 1 minute to 100 hours. The TERP method can obtain a high yield and a precise molecular weight distribution even at a low polymerization temperature and a short polymerization time. At this time, the pressure is usually set at normal pressure, but may be increased or decreased.

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

The growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR ⁴¹ derived from a tellurium compound (where R ⁴¹ is the same as above), and is inactivated by the operation in air after the completion of the polymerization reaction. However, tellurium atoms may remain. Since the copolymer having a tellurium atom at the terminal is colored or has poor 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, a polymer adsorbent, etc .; A method for adsorbing a metal: a peroxide such as hydrogen peroxide or benzoyl peroxide is added, or air or oxygen is blown into the system to oxidize and decompose the tellurium atom at the terminal of the copolymer, and to wash with water or an appropriate solution. A liquid-liquid extraction method or a solid-liquid extraction method for removing residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration for extracting and removing only those having a specific molecular weight or less; Also, these methods can be used in combination.

  When the tertiary amine group of the structural unit represented by the formula (3) is quaternized, the quaternizing agent may be a sulfate compound represented by the formula (6-1) or a sulfuric acid compound represented by the formula (6-2). Sulfonic acid compounds to be used.

〔式（６−１）中、Ｒ²¹およびＲ²³は、アルキル基もしくは芳香族基を示す。
式（６−２）中、Ｒ²²およびＲ²⁴は、アルキル基もしくは芳香族基を示す。〕

[In the formula (6-1), R ²¹ and R ²³ represent an alkyl group or an aromatic group.
In the formula (6-2), R ²² and R ²⁴ represent an alkyl group or an aromatic group. ]

Examples of the alkyl group represented by R ^{21 to} R ²⁴ include a straight-chain alkyl group, a branched-chain alkyl group, and a cyclic alkyl group. A straight-chain alkyl group having 1 to 20 carbon atoms is more preferable. Is a linear alkyl group having 1 to 10 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. In the formula (6-1), R ²¹ and R ²³ are preferably the same substituent.

Examples of the aromatic group represented by R ^{21 to} R ²⁴ include an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group, and the like. ~ 12 aromatic ring groups are preferred. Specific examples include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthalene group.

  Examples of the sulfate compound include dimethyl sulfate, methyl ethyl sulfate, diethyl sulfate, di-n-propyl sulfate, methyl-n-propyl sulfate, methyl isopropyl sulfate, ethyl-n-propyl sulfate, di-n-butyl sulfate, and methyl sulfate. -N-butyl, ethyl sulfate-n-butyl, n-propylbutyl sulfate, diphenyl sulfate, methylphenyl sulfate, ethylphenyl sulfate and the like. Among these, dialkyl sulfate is preferred, and dimethyl sulfate and diethyl sulfate are particularly preferred.

  Examples of the sulfonic acid compound include methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, isopropyl methanesulfonate, ethyl benzenesulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate and p-toluenesulfonate. -Ethyl toluenesulfonate and the like. Among these, aromatic sulfonic acids having an aromatic ring are preferred, and methyl p-toluenesulfonate and ethyl p-toluenesulfonate are particularly preferred.

  Examples of a method of quaternizing a part of the tertiary amine structure of the structural unit represented by the formula (3) in the polymer include a method of contacting the polymer with a quaternizing agent. Specifically, after polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (3), a quaternizing agent is added to the reaction solution, followed by stirring. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 25C to 65C, and the stirring time is preferably 1 hour 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, and a mixed solvent of a solvent and a protic solvent that can be used for the polymerization reaction, and the solubility of the target block copolymer. May be selected as appropriate.

<Dispersant>
The dispersant of the present invention contains the block copolymer as a main component (50% by mass or more), preferably contains 75% by mass or more of the block copolymer, and more preferably contains the block copolymer. It is composed of only a block copolymer. In the block copolymer, for example, a tertiary amino group and a quaternary ammonium group in the structure (B block) are firmly bonded to an acidic group of a coloring material treated with an acidic coloring material or an acidic group-containing dye derivative. However, it is considered that the action of enhancing the dispersibility of the colorant is exhibited by the adsorption of the B block onto the colorant. That is, since the dispersant of the present invention is a component that disperses the colorant satisfactorily by this action, the type of the colorant to be dispersed is not particularly limited. Since the coloring composition using the dispersant of the present invention has alkali developability, it can be suitably used as a dispersant for color filters.

<Coloring composition>
The coloring composition of the present invention contains the above dispersant, coloring material, dispersion medium and binder resin.

(Coloring material)
The type of the coloring material may be appropriately selected according to its use, and examples thereof include pigments and dyes. It is preferable that the coloring composition contains a pigment as a coloring material from the viewpoint of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable. Examples of the pigment include pigments of each color such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a violet pigment. Pigment structures include azo pigments such as monoazo pigments, diazo pigments, and condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo And polycyclic pigments such as thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The coloring material contained in the coloring composition may be only one type, or may be a plurality of types for adjusting chromaticity or the like.

  Specific examples of the pigment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 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, 185, 188, 193, 194, 213; I. Orange pigments such as CI Pigment Orange 36, 38 and 43; I. Blue pigments such as C.I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60; I. Green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, 63; I. Violet pigments such as CI Pigment Violet 23, 29, 32, and 50. Pigments are, among these, 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, C.I. I. Pigment Green 59 and the like are preferable.

  When a light-shielding material such as a black matrix of a color filter is formed using the coloring composition of the present invention, a black pigment can be used. The black pigment may be used alone, or the red pigment, the green pigment, the blue pigment, and the like may be mixed and used. Examples of the black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoint of light blocking ratio and image characteristics.

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

  The coloring material may contain a pigment derivative as a dispersion aid. The dye derivative preferably contains an acidic dye derivative having an acidic group in order to be ionically bonded and adsorbed to a tertiary amino group or a quaternary ammonium base in the block copolymer contained in the dispersant. . This dye derivative has an acidic functional group introduced into the dye skeleton. As the dye skeleton, a skeleton that is the same or similar to the coloring material constituting the coloring composition, or a skeleton that is the same or similar to the compound that is a raw material of the pigment is preferable. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, and a perylene dye skeleton. As the acidic group introduced into the dye skeleton, a carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable. In addition, a sulfonic acid group is preferable on account of the synthesis and the strength of the acidity. The acidic group may be directly bonded to the dye skeleton, or may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, an ether, a sulfonamide, or a urethane bond. The amount of the dye derivative used is not particularly limited, but is preferably, for example, 4 parts by mass to 17 parts by mass with respect to 100 parts by mass of the coloring material.

  From the viewpoint of luminance, the upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and more preferably 60% by mass in the total solid content of the coloring composition. Is more preferable. In addition, the lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass in the total solid content of the coloring composition. preferable. Here, the solid content is a component other than the dispersion medium described below.

  The content of the dispersant with respect to the colorant in the coloring composition is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and is preferably 10 parts by mass with respect to 100 parts by mass of the colorant. More preferably, the amount is from 80 parts by mass to 80 parts by mass.

(Dispersion medium)
The coloring composition is appropriately selected as a dispersion medium, as long as it disperses or dissolves other components constituting the coloring composition, and does not react with these components and has appropriate volatility. Can be used. For example, conventionally known organic solvents can be used, and glycol monoalkyl ethers, glycol dialkyl ethers, glycol alkyl ether acetates, glycol diacetates, alkyl acetates, ethers, ketones, monovalent or polyhydric alcohols can be used. Polyhydric alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chain or cyclic esters, alkoxycarboxylic acids, halogenated hydrocarbons, ether ketones, nitriles, etc. .

  Glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene Glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl- 3-methoxy Pentanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and the like. Examples of the glycol dialkyl ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, and the like. As glycol alkyl ether acetates, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol mono Chill ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and the like. Examples of glycol diacetates include ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and the like. Examples of the alkyl acetates include cyclohexanol acetate. Examples of ethers include amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether and the like. Ketones include 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, methoxy Methyl pentanone and the like. Examples of monohydric or polyhydric alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1-methoxy-2-propanol, and methoxymethyl. Pentanol, glycerin, benzyl alcohol and the like can be mentioned. Examples of the aliphatic hydrocarbons include n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane, and the like. Examples of the alicyclic hydrocarbons include cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl, and the like. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, cumene and the like. As chain or cyclic esters, amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate , Isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Examples thereof include propyl propionate, butyl 3-methoxypropionate, and γ-butyrolactone. Examples of the alkoxycarboxylic acids include 3-methoxypropionic acid and 3-ethoxypropionic acid. Examples of the halogenated hydrocarbon include butyl chloride, amyl chloride and the like. Examples of ether ketones include methoxymethylpentanone. Nitriles include acetonitrile, benzonitrile and the like. The organic solvent should be glycol alkyl ether acetates, glycol monoalkyl ethers, monohydric or polyhydric alcohols from the viewpoints of dispersibility of the coloring material, dispersant solubility, and coating properties of the coloring composition. Is preferred. The solvent contained in the coloring composition may be only one type or a plurality of types.

  In the case of forming pixels of a color filter by a photolithography method, the boiling point of the dispersion medium is preferably from 100 ° C to 200 ° C (under a pressure of 1013.25 hPa; hereinafter, all boiling points are the same), and preferably from 120 ° C to 170 ° C. More preferred. Among the dispersing media, glycol alkyl ether acetates are preferable because they have good balance between coatability and surface tension, and have relatively high solubility of the components in the coloring composition. The glycol alkyl ether acetates may be used alone or in combination with another dispersion medium. In this case, it is also preferable to use a dispersion medium having a boiling point of 150 ° C. or higher. By using such a dispersion medium having a high boiling point in combination, the coloring composition becomes difficult to dry, and the destruction of the mutual relationship between the coloring compositions due to rapid drying can be suppressed. The content of the dispersion medium having a boiling point of 150 ° C. or higher is preferably 3% by mass to 50% by mass based on 100% by mass of the entire dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress the deposition and solidification of the coloring material and the like at the tip of the slit nozzle and the generation of foreign matter defects. When the content is 50% by mass or less, the drying speed of the coloring composition becomes slow, and it is possible to suppress the occurrence of problems such as prolonged drying time and pin marks of prebaking in the production of a color filter described later. The dispersion medium having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates. In this case, a dispersion medium having a boiling point of 150 ° C. or higher may not be separately contained.

  When pixels of a color filter are formed by an inkjet method, the boiling point of the dispersion medium is preferably from 130 ° C to 300 ° C, more preferably from 150 ° C to 280 ° C. By setting the boiling point to 130 ° C. or higher, the uniformity of the obtained coating film is improved. Further, by setting the boiling point to 300 ° C. or lower, the residual solvent in the coating film after the thermal baking can be reduced, and defects in quality and prolonged drying time can be suppressed. Further, the vapor pressure of the dispersion medium may be generally 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of uniformity of the obtained coating film.

  In the production of a color filter by the ink-jet method, the ink emitted from the nozzle is very fine, several pL to several tens of pL. Tend to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the dispersion medium is high, and specifically, it is preferable to include a dispersion medium having a boiling point of 180 ° C. or higher. More preferably, it contains a dispersion medium having a boiling point of at least 200 ° C, particularly preferably at least 220 ° C. Further, the high boiling point solvent having a boiling point of 180 ° C. or more is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 90% by mass, based on 100% by mass of the entire dispersion medium contained in the colored resin composition. % Or more is most preferable. When the ratio is equal to or more than the lower limit, the effect of preventing the solvent from evaporating from the droplet tends to be sufficiently exerted.

  The content of the dispersion medium in the coloring composition is not particularly limited, and can be appropriately adjusted. The upper limit of the content of the dispersion medium in the coloring composition is usually 99% by mass. In addition, the lower limit of the content of the dispersion medium in the coloring composition is usually 70% by mass, and preferably 75% by mass, in consideration of the viscosity suitable for applying the coloring composition. The dispersion medium can be used as a solvent for dissolving and removing the precipitate formed from the coloring composition.

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

  Preferred embodiments of the binder resin include a random copolymer containing styrene and a structural unit derived from a carboxy group-containing vinyl monomer, a structural unit derived from (meth) acrylate, and a structural unit derived from a carboxy group-containing vinyl monomer. And a random copolymer containing a structural unit derived from (meth) acrylate. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono ( (Meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like. That.

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

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

  In the copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate, the content of (meth) acrylic acid is usually from 5% by mass to 90% by mass, and preferably from 10% by mass to 70% by mass, based on all monomer components. And more preferably 20 to 70% by mass.

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

  Mw of the binder resin 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 and the film strength of the colored layer formed from the colored composition are improved, and when the Mw is 100,000 or less, the alkali developability of the coating film is improved. Is further improved.

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

  The binder resin contained in the coloring composition may be only one type or a plurality of types. In the coloring 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, and more preferably 20 parts by mass with respect to 100 parts by mass of the coloring material. More preferably, the amount is from 80 parts by mass to 80 parts by mass.

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

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

  Examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher valent compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, glycerol dimethacrylate and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; pyromellitic anhydride, biphenyltetracarboxylic acid Tetraacid dianhydrides such as acid dianhydride and benzophenonetetracarboxylic dianhydride are exemplified.

  In the coloring composition of the present invention, the content of the crosslinking agent is preferably from 10 parts by mass to 1,000 parts by mass, particularly preferably from 20 parts by mass to 500 parts by mass, per 100 parts by mass of the coloring material. If the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the amount of the cross-linking agent is too large, the alkali developability of the coloring composition of the present invention is reduced, and background contamination on the unexposed portion of the substrate or the light-shielding layer, a film residue, and the like tend to be easily generated. .

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

  Examples of the photopolymerization initiator include, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones Compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and the like. The photopolymerization initiators can be used alone or in combination of two or more.

  In the colored composition of the present invention, the content of the photopolymerization initiator is preferably from 0.01 to 120 parts by mass, particularly preferably from 1 to 100 parts by mass, based on 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, the curing may be insufficient due to exposure, while if it is too large, the formed colored layer tends to fall off the substrate at the time of development and tend to be difficult. .

(Other additives)
The coloring composition may contain other additives in addition to the additives as long as the preferable physical properties of the present invention are not impaired. Other additives include dispersants other than the block copolymer, sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, Plasticizers, organic carboxylic acid compounds, organic carboxylic anhydrides, pH adjusters, antioxidants, ultraviolet absorbers, light stabilizers, preservatives, fungicides, anti-agglomeration agents, adhesion improvers, development improvers, Storage stabilizers and the like can be mentioned.

  Examples of the dispersant excluding the block copolymer include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and fats. Group-modified polyester dispersants and the like.

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

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

  Nonionic surfactants include fluorine surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra Fluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like) Surfactants, polyoxyethylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene Fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrit fatty acid esters, polyoxyethylene pentaerythrit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters , Polyoxyethylene sorbite fatty acid esters, etc.).

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

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

  Examples of the organic carboxylic acid compound include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, oxalic acid, malonic acid, succinic acid, and glutaric acid. Carboxyl groups were directly bonded to phenyl groups such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarballylic acid, aconitic acid, benzoic acid and phthalic acid Examples thereof include carboxylic acids and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond.

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

<Method for producing colored composition and color filter>
The coloring composition can be prepared by mixing a dispersant (block copolymer), a coloring material, a dispersion medium, a binder resin, and, if necessary, a crosslinking agent, a photopolymerization initiator, and other additives. For mixing, for example, a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, and a kneader can be used. It is preferable that the coloring composition is filtered after mixing.

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

  The color filter of the present invention includes a coloring layer formed using the coloring composition. As a method of manufacturing a color filter, for example, the following method can be mentioned. First, thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin and polymethyl methacrylate resin, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, poly (meth) acrylic resin, and various types of glass For example, after applying the coloring composition of the present invention in which a red pigment is dispersed on a transparent substrate such as the above, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, the coating film is exposed through a photomask, and then developed using an alkali developing solution (such as an aqueous solution containing an organic solvent or a surfactant and an alkaline compound) to dissolve and remove unexposed portions of the coating film. I do. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed. Next, using each colored composition of green or blue, in the same manner as described above, coating, pre-baking, exposure, development and post-baking of each colored composition are performed to form a green pixel array and a blue pixel array on the same substrate. Formed sequentially on top. Thereby, a color filter in which pixel arrays of three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above. Further, a black matrix may be provided on a transparent substrate used for forming a pixel array of three primary colors of red, green and blue.

When applying the coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, and a bar coating method can be used. In particular, it is preferable to employ a spin coating method or a slit die coating method.
After a protective film is formed on the pixel pattern thus obtained, if necessary, a transparent conductive film (such as ITO) is formed by sputtering. After the formation of the transparent conductive film, a spacer may be further formed to form a color filter.

  The color filter of the present invention has high dimensional accuracy and the like, and can be suitably used for a color liquid crystal display device, a color image pickup tube device, a color sensor, an organic EL display device, electronic paper, and the like.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these specific examples. Various physical properties were measured by the following instruments. The meanings of the abbreviations are as follows.
MMA: methyl methacrylate BMA: n-butyl methacrylate EHMA: 2-ethylhexyl methacrylate M9EGM: methoxypolyethylene glycol monomethacrylate (additional mole number of ethylene oxide: 9) (trade name: Blemmer (registered trademark) PME-400, manufactured by NOF Corporation)
M4EGM: methoxypolyethylene glycol monomethacrylate (additional mole number of ethylene oxide: 4) (trade name: Blemmer (registered trademark) PME-200, manufactured by NOF Corporation)
PCL5: 5-hydroxycaprolactone adduct of 2-hydroxyethyl methacrylate (Placel (registered trademark) FM5, manufactured by Daicel Chemical Industries, Ltd.)
MAA: DMAEMA methacrylate: 2- (dimethylamino) ethyl methacrylate DMAPMAm: N- (3-dimethylaminopropyl) methacrylamide BTEE: Ethyl-2-methyl-2-n-butylteranyl-propionate DBDT: dibutyl ditelluride AIBN : 2,2'-azobis (isobutyronitrile)
ADVN: Azobis (2,4-dimethylvaleronitrile)
Me ₂ SO ₄ : dimethyl sulfate MePTSA: methyl p-toluenesulfonate BzCl: benzyl chloride PMA: propylene glycol monomethyl ether acetate MP: 1-methoxy-2-propanol

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

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It was determined by gel permeation chromatography (GPC) using a high performance liquid chromatograph (manufactured by Tosoh Corporation, model: HLC-8320). The column used was one SHOdex KF-603 (Φ6.0 mm × 150 mm) (manufactured by SHOdex), 30 mmol / L lithium bromide-30 mmol / L acetate-N-methylpyrrolidone solution as the mobile phase, and a differential refractometer as the detector. used. The measurement conditions were as follows: the column temperature was 40 ° C., the sample concentration was 10 mg / mL, the sample injection amount was 10 μL, and the flow rate was 0.2 mL / min. A calibration curve (calibration curve) was prepared using polystyrene (molecular weight 70,500, 37,900, 19,920, 10,200, 4,290, 2,630, 1,150) as a standard substance, and the weight average was calculated. The molecular weight (Mw) and the number average molecular weight (Mn) were measured. The molecular weight distribution (PDI = Mw / Mn) was calculated from these measured values.

(Amine value)
The amine value is represented by the mass of potassium hydroxide (KOH) equivalent to the basic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated by the following equation using the inflection point of the titration pH curve as the end point of the titration.
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 used for titration (mL)
f: titer of 0.1 mol / L hydrochloric acid / 2-propanol solution w: mass (g) of the measurement sample (solid content conversion)

(Acid value)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, a few drops of a phenolphthalein ethanol solution were added as an indicator, and neutralization titration was performed with a 0.1 mol / L potassium hydroxide / ethanol solution. The acid value (A) was calculated by the following equation.
A = 56.11 × Vs × 0.1 × f / w
A: Acid value (mgKOH / g)
Vs: amount of 0.1 mol / L potassium hydroxide / ethanol solution required for titration (mL)
f: titer of 0.1 mol / L potassium hydroxide / ethanol solution w: mass (g) of the measurement sample (in terms of solid content)

(Content of halogen anion)
The sample preparation was performed as follows. About 100 mg of the reaction solution after the quaternization step 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 in the combustion furnace was 15 minutes. Exhaust gas was captured by a collector (trade name: AU-250, manufactured by Mitsubishi Chemical Analytech). Ultrapure water was used as an absorbing solution, and 35 mL of the obtained water absorbing solution was diluted to 50 mL with ultrapure water to prepare a sample solution.
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-12A (manufactured by DIONEX), and the eluent used was an eluent for anion analysis (brand name: AS12A, manufactured by DIONEX). The measurement conditions were a sample injection amount 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 chloride anion concentration of 0.5 ppm, 1 ppm, and 2 ppm as a standard substance, and the chloride anion concentration was calculated.

(Heating weight reduction temperature)
The measurement was performed using a thermogravimetric / differential heat simultaneous measurement device (TG-DTA) (manufactured by HITACHI, TG / DTA6300). The measurement sample was dried under reduced pressure at 130 ° C. for 1 hour 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 mass of the sample decreased by 10% was read from the obtained TG curve, and this was defined as the heating weight reduction temperature.

(viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at 25 ° C. and a rotor rotation speed of 60 rpm using a cone rotor (1 ° 34 ′ × R24). . The measurement was performed on the colored composition stored at 40 ° C. for one week after preparation.

(Alkali developability)
Using a spin coater (trade name: MS-A100, manufactured by Mikasa Corporation), a coating film of the coloring composition for a color filter was formed at 2000 rpm for 10 seconds on a 50 mm × 50 mm glass plate whose surface was washed. The test piece was prepared by drying at 10 ° C. for 10 minutes and cutting the glass plate on which the coating film was formed into a shape of 50 mm × 10 mm. Next, the upper end of the test piece in the longitudinal direction was attached to a dip coater (trade name: DC4016, manufactured by Eiden Co., Ltd.), and the portion from the lower end in the longitudinal direction of the test piece to 42.5 mm was washed with a potassium hydroxide aqueous solution (concentration: 0.2% by mass), the test piece was pulled up at a speed of 0.22 mm / s, and the distance until the coating film was dissolved was measured.
The development time (second) was calculated by the following equation.
T = X / 0.22
T: Development time (second)
X: distance to dissolution

<Production of quaternary copolymer>
(No.1)
MMA (99.9 g), BMA (64.8 g), EHMA (59.5 g), M9EGM (21.6 g), AIBN (0.74 g), PMA (163) were placed in a flask equipped with an argon gas inlet tube and a stirrer. 8.8 g), and after purging with argon, BTEE (7.09 g) and DBDT (2.50 g) were added and reacted at 60 ° C. for 16 hours to polymerize the first block. The conversion was 98%.

  To the reaction solution, a mixed solution of DMAEMA (87.8 g), AIBN (0.62 g), and PMA (58.5 g), which had been purged with argon in advance, was added and reacted at 60 ° C. for 20 hours to polymerize the second block. The polymerization rate of DMAEMA was 99%. Further, the monomer for the first block remaining in the reaction solution was also polymerized and taken into the second block. The polymerization rate of the first block monomer remaining in these reaction solutions was 100%. The content of each structural unit in the copolymer was calculated from the charged ratio and the conversion of the monomers used in the polymerization reaction.

  After the completion of the reaction, the reaction solution was poured into stirring n-heptane. The precipitated polymer was filtered by suction and dried to obtain a quaternized copolymer.

(No. 2-5)
The copolymer before quaternization No. In the same manner as in the production method of No. 1, copolymer No. 4 before quaternization was used. 2 to 5 were produced. Table 1 shows the raw material monomers, organic tellurium compounds, organic ditelluride compounds, azo-based polymerization initiators, solvents, reaction conditions, and polymerization rates used. The content of each structural unit in the copolymer was calculated from the charged ratio and the conversion of the monomers used in the polymerization reaction.

(No. 6)
In a flask equipped with an argon gas inlet tube and a stirrer, MMA (4.23 g), BMA (2.74 g), EHMA (2.52 g), M9EGM (0.91 g), DMAPMAm (3.71 g), n- Dodecanethiol (0.28 g) and PMA (21.0 g) were charged, and after purging with argon, the temperature was raised to 78 ° C. While maintaining the solution at 78 ° C., the solution was added to MMA (8.45 g), BMA (5.48 g), EHMA (5.03 g), M9EGM (1.83 g), DMAPMAm (7.43 g), ADVN (0 .85 g), n-dodecanethiol (0.56 g) and PMA (42.3 g) were added dropwise over 1.5 hours. 60 minutes after the completion of the dropwise addition, while maintaining the temperature at 78 ° C., ADVN (0.11 g) and PMA (2.0 g) were added and reacted for 1 hour. Further, ADVN (0.11 g) and PMA (2.0 g) were added and reacted for 1 hour. Further, ADVN (0.11 g) and PMA (2.0 g) were added and reacted for 1 hour. Further, ADVN (0.11 g) and PMA (2.0 g) were added and reacted for 2 hours. The obtained reaction solution was cooled to room temperature, and copolymer No. 4 before quaternization was obtained. 6 were obtained. The nonvolatile content was 34.9%.

(No. 7)
Except that DMAPMAm was changed to DMAEMA, copolymer No. 4 before quaternization was used. 6 in the same manner as in the production method of Copolymer No. 6 7 was obtained. The nonvolatile content was 35.4%.

<Quaternizing process of copolymer>
The quaternized copolymer was dissolved in PMA or a mixed solvent of PMA / MP (PMA: MP = 1: 1 (mass ratio)) to prepare a PMA solution or a PMA / MP solution. The PMA solution or PMA / MP solution of the obtained quaternized copolymer was placed in an eggplant flask. To this solution, dimethyl sulfate (a reagent manufactured by Tokyo Chemical Industry), methyl p-toluenesulfonate (a reagent manufactured by Tokyo Chemical Industry) or benzyl chloride was added dropwise while stirring at room temperature. Thereafter, the mixture was stirred and reacted at 60 ° C. This was cooled to obtain a quaternized block copolymer solution. Tables 3 and 4 show quaternizing agents, solvents, and reaction conditions used in the quaternizing step. Tables 5 and 6 show the composition, Mw, PDI, amine value, and acid value of the quaternized copolymer.

  Copolymer no. 1 to 7 have an A block having no structural unit of the general formula (1) and a B block having a structural unit of the general formula (1). Copolymer no. Nos. 8 to 12 are cases where the counter anion of the B block is a chloride ion. Comparing the copolymers having the same composition of the quaternary polymer with respect to each of these copolymers, the counter ion of the B block is represented by the formula (Copolymer Nos. 8 to 12) more than the chloride ion (Copolymer Nos. 8 to 12). 2-1) or those represented by the formula (2-2) (Copolymer Nos. 1 to 7) have a higher heating weight loss temperature and are superior in heat resistance.

  Copolymer no. 13 and 14 are random copolymers, and the counter ion of the quaternary ammonium base is a sulfate ion. Copolymer No. 1 in which the same monomers are used. 1 and copolymer No. 1 14 is a block copolymer. It can be seen that No. 1 has a higher heating weight reduction temperature and is superior in heat resistance.

<Production of coloring composition>
(Manufacture of binder resin)
MAA (20.0 g), BzMA (80.0 g), PMA (290.0 g) were charged into a flask equipped with an argon gas inlet tube and a stirrer, and after purging with argon, AIBN (1.5 g), n-dodecane Thiol (2.0 g) and PMA (10.0 g) were added, and the temperature was raised to 90 ° C. While maintaining the solution at 90 ° C., MAA (40.0 g), BzMA (160.0 g), AIBN (3.0 g), n-dodecanethiol (4.0 g), and PMA (25.0 g) were added to the solution. It was added dropwise over 1.5 hours. After 60 minutes from the completion of the dropping, the temperature was raised to 110 ° C., AIBN (0.3 g) and PMA (5.0 g) were added, and the mixture was reacted for 1 hour. Further, AIBN (0.3 g) and PMA ( 5.0 g) was added and reacted for 1 hour. AIBN (0.3 g) and PMA (5.0 g) were further added and reacted for 1 hour.

  The obtained reaction solution was cooled to room temperature, PMA (120.0 g) was added, and a solution of a binder resin having a nonvolatile content of 40% was obtained. The binder resin had a weight average molecular weight (Mw) of 14,760, a molecular weight distribution (PDI) of 1.87, and an acid value of 131 mgKOH / g.

(Coloring composition)
8 parts by mass of a pigment, 4 parts by mass of a quaternized copolymer as a dispersant, 5 parts by mass of a binder resin, and 83 parts by mass of PMA were blended. To this mixture, 560 parts by mass of 0.3 mm zirconia beads are added, mixed for 2 hours with a bead mill (trade name: DISPERMAT CA, manufactured by VMA-GETZMANN GmbH), sufficiently dispersed, and the average particle diameter of the pigment after dispersion is obtained. Was 100 nm. After completion of the dispersion, the beads were filtered off to obtain a colored composition. Pigments in the preparation of the blended liquid include C.I. I. Pigment Blue 15: 6 (trade name: FASTOGEN BLUE EP, manufactured by DIC) was used. The solution of the quaternized block copolymer produced above was used as the quaternized copolymer in the preparation of the mixture. The binder resin solution obtained above was used as the binder resin in the preparation of the mixture.

(Coloring composition for color filter)
66 parts by mass of the obtained coloring composition, 8 parts by mass of a binder resin, and 3 parts by mass of a crosslinking agent (polyfunctional monomer, trade name: NK ester A-DPH (dipentaerythritol hexaacrylate), manufactured by Shin-Nakamura Chemical Co., Ltd.) A coloring composition for a color filter was prepared with a composition of 2 parts by mass of a photopolymerization initiator (trade name: Irgacure 184, manufactured by Tokyo Chemical Industry Co., Ltd.) and 21 parts by mass of PMA. The binder resin solution obtained above was used as the binder resin in the preparation of the coloring composition for color filter.

  Coloring composition No. Coloring compositions for color filters using Nos. 1 to 7 are copolymer Nos. 1 to 3 as dispersants. Contains 1 to 7. These coloring compositions for color filters had a low viscosity even after one week, and also had excellent alkali developability. In particular, as a dispersant, copolymer No. A in which A block has an acidic group The coloring compositions for color filters using Nos. 2 and 3 were more excellent in alkali developability despite the low quaternization ratio.

  Coloring composition No. Coloring compositions for color filters using Nos. 8 to 12 are copolymer No. 8 as dispersants. 8-12 are contained. These coloring compositions for color filters have low viscosity even after one week. In addition, these coloring compositions for a color filter are copolymer Nos. Since the heat resistance of 8 to 12 is low, it is considered that the heat resistance of the obtained color filter is low.

  Coloring composition No. Coloring compositions for color filters using Nos. 13 and 14 are copolymer Nos. Contains 13 or 14. These coloring compositions for color filters gelled one week after preparation. Therefore, the copolymer No. 13 and 14 have poor dispersion stability.

The present invention includes the following embodiments.
(Embodiment 1)
It has an A block and a B block, and the A block contains a structural unit derived from a (meth) acrylic vinyl monomer, and contains a structural unit represented by the following general formula (1) in the A block. A block copolymer having a ratio of less than 5% by mass and a content of a structural unit represented by the following general formula (1) in the B block of 5% by mass or more.

〔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。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２−１）または一般式（２−２）で表される対イオンを示す。
式（２−１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２−２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. R ¹⁵ represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by the general formula (2-1) or (2-2).
In the formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In the formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

(Embodiment 2)
The block copolymer according to embodiment 1, wherein the B block further contains a structural unit represented by the following general formula (3).

〔式（３）において、Ｒ³¹およびＲ³²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およびＲ³²は互いに結合して環状構造を形成していてもよい。Ｒ³³は、鎖状の２価の炭化水素基を示す。Ｒ³⁴は、水素原子またはメチル基を示す。〕

[In the formula (3), R ³¹ and R ³² each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a chain divalent hydrocarbon group. R ³⁴ represents a hydrogen atom or a methyl group. ]

(Embodiment 3)
The block copolymer according to embodiment 1 or 2, wherein the content of the structural unit represented by the formula (1) is 5% by mass to 90% by mass in 100% by mass of the B block.

(Embodiment 4)
The block copolymer according to any one of Embodiments 2 and 3, wherein the content of the structural unit represented by the formula (3) is 10% by mass to 95% by mass in 100% by mass of the B block. .

(Embodiment 5)
The (meth) acrylic vinyl monomer has a (meth) acrylate having a chain alkyl group, a (meth) acrylate having a cyclic alkyl group, a (meth) acrylate having an aromatic group, and a (meth) acrylate having a polyalkylene glycol structural unit. A) acrylate, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, (meth) acrylate having an alkoxy group, (meth) acrylate having an oxygen-containing heterocyclic group, and (meth) acrylate having an acidic group. 5.) The block copolymer according to any one of embodiments 1 to 4, wherein the block copolymer is at least one monomer selected from the group consisting of acrylate and (meth) acrylic acid.

(Embodiment 6)
The block copolymer according to any one of Embodiments 1 to 5, wherein the A block includes a structural unit represented by the following general formula (7).

〔一般式（７）において、ｎ７は２〜１５０の整数を表す。Ｒ⁷¹は水素原子又は炭素数が１〜６のアルキル基を表す。Ｒ⁷²は炭素数が１〜６のアルキレン基を表す。Ｒ⁷³は水素原子またはメチル基を表す。〕

[In the general formula (7), n7 represents an integer of 2 to 150. R ⁷¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁷² represents an alkylene group having 1 to 6 carbon atoms. R ⁷³ represents a hydrogen atom or a methyl group. ]

(Embodiment 7)
The block copolymer according to embodiment 6, wherein the content of the structural unit represented by the formula (7) is 5% by mass to 60% by mass in 100% by mass of the A block.

(Embodiment 8)
The block copolymer according to any one of embodiments 1 to 7, wherein the A block includes a structural unit represented by the following general formula (8).

〔一般式（８）において、ｎ８は１〜１０の整数を表す。Ｒ⁸¹は炭素数が１〜１０のアルキレン基を表す。Ｒ⁸²は炭素数が１〜１０のアルキレン基を表す。Ｒ⁸³は水素原子またはメチル基を表す。〕

[In the general formula (8), n8 represents an integer of 1 to 10. R ⁸¹ represents an alkylene group having 1 to 10 carbon atoms. R ⁸² represents an alkylene group having 1 to 10 carbon atoms. R ⁸³ represents a hydrogen atom or a methyl group. ]

(Embodiment 9)
The block copolymer according to embodiment 8, wherein the content of the structural unit represented by the formula (8) is 5 mass% to 80 mass% in 100 mass% of the A block.

(Embodiment 10)
The block copolymer according to any one of Embodiments 1 to 9, wherein the content of the structural unit derived from the (meth) acrylic vinyl monomer is 80% by mass or more in 100% by mass of the A block.

(Embodiment 11)
The block copolymer according to any one of Embodiments 1 to 10, wherein the mass ratio between the A block and the B block (A block / B block) in the block copolymer is 50/50 to 95/5. .

(Embodiment 12)
The block copolymer according to any one of embodiments 1 to 11, wherein the amine value of the block copolymer is 10 mgKOH / g to 200 mgKOH / g.

(Embodiment 13)
The block copolymer according to any one of embodiments 1 to 12, wherein the acid value of the block copolymer is 5 mgKOH / g to 50 mgKOH / g.

(Embodiment 14)
The block copolymer according to any one of embodiments 1 to 13, which is an AB type diblock copolymer or an ABA type triblock copolymer.

(Embodiment 15)
The block copolymer according to any one of embodiments 1 to 14, wherein the molecular weight distribution (PDI) of the block copolymer is 2.2 or less.

(Embodiment 16)
The block copolymer according to any one of Embodiments 1 to 15, wherein the weight average molecular weight (Mw) of the block copolymer is 3,000 to 40,000.

(Embodiment 17)
The block copolymer according to any one of embodiments 1 to 16, wherein the block copolymer is polymerized by living radical polymerization.

(Embodiment 18)
A dispersant comprising the block copolymer according to any one of embodiments 1 to 17.

(Embodiment 19)
Embodiment 19. The dispersant according to embodiment 18, which is used for a color filter.

(Embodiment 20)
A coloring composition comprising the dispersant, a coloring agent, a dispersion medium and a binder resin according to embodiment 18 or 19.

(Embodiment 21)
A color filter comprising a coloring layer formed using the coloring composition according to embodiment 20.

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

Claims (16)

A dispersant containing a block copolymer,
The block copolymer is an ABA triblock copolymer having an A block and a B block,
The content of the B block is 5% by mass or more in 100% by mass of the entire block copolymer;
The A block contains a structural unit derived from a (meth) acrylic vinyl monomer, and the content of the structural unit represented by the following general formula (1) in the A block is less than 5% by mass;
The content of the structural unit represented by the following general formula (1) in the B block is 5% by mass to 90% by mass,
The content of the structural unit represented by the following general formula (3) in the B block is 10% by mass to 95% by mass,
The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) in the B block is 80% by mass or more;
A dispersant, wherein the content of a halogen anion in the block copolymer is 10 ppm or less.

[In the formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. R ¹⁵ represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by the general formula (2-1) or (2-2).
In the formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In the formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

[In the formula (3), R ³¹ and R ³² each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a chain divalent hydrocarbon group. R ³⁴ represents a hydrogen atom or a methyl group. ]   The mass ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (3) in the B block (the structural unit represented by the formula (1) / the structural unit represented by the formula (3)) The dispersant according to claim 1, wherein the structural unit is 30/70 to 90/10.   The dispersant according to claim 2, wherein the content of the block copolymer in the dispersant is 50% by mass or more.   The (meth) acrylic vinyl monomer has a (meth) acrylate having a chain alkyl group, a (meth) acrylate having a cyclic alkyl group, a (meth) acrylate having an aromatic group, and a (meth) acrylate having a polyalkylene glycol structural unit. A) acrylate, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, (meth) acrylate having an alkoxy group, (meth) acrylate having an oxygen-containing heterocyclic group, and (meth) acrylate having an acidic group. The dispersant according to any one of claims 1 to 3, which is at least one monomer selected from the group consisting of)) acrylate and (meth) acrylic acid.   The dispersant according to any one of claims 1 to 4, wherein the content of the structural unit derived from the (meth) acrylic vinyl monomer is 80% by mass or more in 100% by mass of the A block.   The dispersant according to any one of claims 1 to 5, wherein the mass ratio of the A block to the B block (A block / B block) in the block copolymer is 50/50 to 95/5.   The dispersant according to any one of claims 1 to 6, wherein the amine value of the block copolymer is 10 mgKOH / g to 200 mgKOH / g.   The dispersant according to any one of claims 1 to 7, wherein the block copolymer has a molecular weight distribution (PDI) of 2.2 or less.   The dispersant according to any one of claims 1 to 8, wherein the block copolymer has a weight average molecular weight (Mw) of 3,000 to 40,000. The (meth) acrylic vinyl monomer is a (meth) acrylate having a hydroxy group, a (meth) acrylate having a lactone-modified hydroxy group, a (meth) acrylate having an oxygen-containing heterocyclic group, a (meth) acrylate having an acidic group The dispersant according to any one of claims 4 to 9 , wherein the dispersant is at least one monomer selected from the group consisting of and (meth) acrylic acid. The (meth) acrylic vinyl monomer has a (meth) acrylate having a lactone-modified hydroxy group,
The content of the structural unit derived from (meth) acrylate having a lactone-modified hydroxy group, wherein the A block 100 mass%, 5 mass% or more, one or more of claims 1 to 10 is 90 wt% or less The dispersant according to item. The A block has a structural unit derived from a vinyl monomer having an acidic group,
The content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more and 20% by mass or less in 100% by mass of the A block, The content according to any one of claims 1 to 11 . Dispersant. The block copolymer has an acidic group,
The dispersant according to any one of claims 1 to 12 , wherein the block copolymer has an acid value of 5 mgKOH / g to 50 mgKOH / g. The dispersant according to claim 13 , which is used for a color filter. A coloring composition comprising the dispersant, a coloring agent, a dispersion medium, and a binder resin according to claim 1 . A color filter comprising a coloring layer formed using the coloring composition according to claim 15 .