JPWO2020031633A1 - Dispersant composition, coloring composition, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant composition in which the amount of formaldehyde generated with time is small.
A dispersant composition is characterized by containing a polymer having a structure represented by the general formula (5) in a side chain.
* -Y ^1- N-R ¹¹ R ¹² (5)
[In the general formula (5), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. Y ¹ represents a divalent hydrocarbon group. * Represents a bond. ]
[Selection diagram] None

Description

The present invention relates to a dispersant composition containing a polymer.

Conventionally, in the production of a color filter used for a liquid crystal display or the like, a dyeing method, a printing method, an inkjet method, an electrodeposition method, a pigment dispersion method and the like are known as methods for applying a coloring material to a base material. Among these, the pigment dispersion method is the mainstream from the viewpoints of spectral characteristics, durability, pattern shape and accuracy. In this pigment dispersion method, a coating film composed of a coloring composition in which a pigment, a dispersant, a dispersion medium (solvent), a binder resin and the like are mixed is formed on a substrate, and radiation is emitted through a photomask having a desired pattern shape. It is irradiated and cured, and alkaline development is performed.

In recent years, increasing the concentration of pigments in coloring compositions has been studied in order to obtain good color reproducibility and high contrast of color filters. When the concentration of the pigment is increased, the proportion of the dispersant is relatively reduced, so that the dispersant is required to have high dispersibility (see, for example, Patent Document 1 (paragraph 0004)). Further, in alkali development, an alkali-soluble binder resin plays a major role. However, in the case of a pigment dispersion composition having a high concentration of pigment, the proportion of the binder resin as a developing component is reduced, and the alkali developability is lowered. Therefore, the alkali developability originally required for the binder resin is also required for the dispersant. As such a dispersant, Patent Document 2 describes an AB block copolymer composed of an A block having a polylactone chain in the side chain and a B block having a tertiary amino group in the side chain as a pigment dispersion. It is described that it is used (see Patent Document 2 (paragraphs 0023 to 0045)).

Japanese Unexamined Patent Publication No. 2009-265515 Japanese Unexamined Patent Publication No. 2013-119568

In the resin type dispersant, it has been proposed to introduce a tertiary amino group into the side chain in order to enhance the dispersibility of the coloring material (see Patent Document 2). However, it is considered that the resin-type dispersant having a tertiary amino group generates formaldehyde over time due to the tertiary amino group. Therefore, when such a resin-type dispersant is used in the coloring composition, formaldehyde is contained in the coloring composition. In recent years, environmental standards have become stricter, so that when a conventional resin-type dispersant is used, the amount of formaldehyde in the coloring composition does not meet the environmental standards.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dispersant composition in which the amount of formaldehyde generated over time is small.

The dispersant composition of the present invention that has been able to solve the above problems is characterized by containing a polymer having a structure represented by the general formula (5) in the side chain.
* -Y ^1- N-R ¹¹ R ¹² (5)
[In the general formula (5), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. Y ¹ represents a divalent hydrocarbon group. * Represents a bond. ]

When a polymer having an amino group is used as a dispersant, it is considered that formaldehyde is generated over time due to this amino group. Surprisingly in the present invention, by forming the amino group into a specific structure (structure represented by the general formula (5)), the generation of formaldehyde over time is suppressed and the formaldehyde in the dispersant composition is reduced. can. Further excellent dispersion performance of the coloring material can be obtained.

The present invention also includes a coloring composition comprising the dispersant composition, a coloring material, a binder resin and a dispersion medium. The present invention also includes a color filter characterized by including a colored layer formed by using the coloring composition.

According to the present invention, a dispersant composition with a small amount of formaldehyde generated over time can be obtained.

Hereinafter, an example of a preferred embodiment in which the present invention has been carried out will be described. However, the following embodiments are merely examples. It is not limited to the following embodiments.

In the present invention, "(meth) acrylic" refers to "at least one of acrylic and methacryl". The "(meth) acrylic monomer" refers to a monomer having a "(meth) acryloyl group" in the molecule. "(Meta) acryloyl" means "at least one of acryloyl and methacryloyl". The "vinyl monomer" refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from the (meth) acrylic monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of the (meth) acrylic monomer is polymerized into a carbon-carbon single bond. The "structural unit derived from a vinyl monomer" means a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized into a carbon-carbon single bond.

<Dispersant composition>
The dispersant composition of the present invention is characterized by containing a polymer having a structure represented by the general formula (5) in the side chain.
* -Y ^1- N-R ¹¹ R ¹² (5)
[In the general formula (5), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. Y ¹ represents a divalent hydrocarbon group. * Represents a bond. ]

When a polymer having an amino group is used as a dispersant, it is considered that formaldehyde is generated over time due to this amino group. Surprisingly in the present invention, by forming the amino group into a specific structure (structure represented by the general formula (5)), the generation of formaldehyde over time is suppressed and the formaldehyde in the dispersant composition is reduced. can. Further excellent dispersion performance of the coloring material can be obtained.

Examples of the chain hydrocarbon group represented by R ¹¹ and R ¹² include a linear alkyl group and a branched chain alkyl group. The linear alkyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms. Examples of the linear alkyl group include an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group and an n-lauryl group. .. The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a neopentyl group, an isooctyl group and the like.

Examples of the substituent contained in the chain hydrocarbon group represented by R ¹¹ and R ¹² include a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H ₅ ), a hydroxy group and the like.

Examples of the cyclic hydrocarbon group represented by R ¹¹ and R ¹² include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion. The cyclic alkyl group preferably has 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. The aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, a mesitylene group and the like. Examples of the chain portion of the cyclic alkyl group having a chain portion and the aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably carbon. The number 1 to 3 alkylene groups can be mentioned.

Examples of the substituent contained in the cyclic hydrocarbon group represented by R ¹¹ and R ¹² include a halogen group, an alkoxy group, a chain alkyl group, a hydroxy group and the like.

Examples of the cyclic structure formed by bonding R ¹¹ and R ¹² to each other include a nitrogen-containing heterocycle having a 5-membered ring to a 7-membered ring or a fused ring formed by condensing two of them. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring.

Examples of the divalent hydrocarbon group represented by Y ¹ include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an arenediyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferable. The alkylene group may be linear or branched, but linear is preferable. Y ¹ is preferably an alkylene group having 1 to 5 carbon atoms.

^{The -N-R 11} R ¹² moiety of the structure represented by the general formula (5) includes a monoalkylamino group such as an ethylamino group, a propylamino group and a tert-butylamino group; a diethylamino group and a dipropylamino group. , Dialkylamino groups such as bis (2-hydroxyethyl) amino groups and the like.

Examples of the polymer having the structure represented by the general formula (5) in the side chain include (meth) acrylic polymers, polyurethane-based polymers, polyester-based polymers, polyallylamine-based polymers, and carbodiimide-based polymers. Can be mentioned.

The amine value of the polymer having the structure represented by the general formula (5) in the side chain is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g, from the viewpoint of adsorptivity to the coloring material and dispersibility of the coloring material. It is g or more, more preferably 80 mgKOH / g or more, preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less.

The molecular weight of the polymer having the structure represented by the general formula (5) in the side chain is measured by gel permeation chromatography. The weight average molecular weight (Mw) of the polymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, particularly preferably 6,000 or more, and 40,000 or less. Is preferable, more preferably 30,000 or less, still more preferably 25,000 or less, and particularly preferably 20,000 or less. When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

(Block copolymer)
From the viewpoint of dispersibility, the polymer has a block copolymer having an A block having a structural unit preferably derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1). Coalescence is preferred.

［一般式（１）において、Ｒ¹¹は、水素原子、置換基を有していてもよい炭素数２以上である鎖状もしくは環状の炭化水素基を表す。Ｒ¹²は、置換基を有していてもよい炭素数２以上である鎖状もしくは環状の炭化水素基を表す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｒ¹³は水素原子またはメチル基を表す。Ｘ¹はアミド基、エステル基、または、単結合を表す。Ｙ¹は２価の炭化水素基を表す。］

[In the general formula (1), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents an amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ]

Various components of the block copolymer and the like will be described below.

(A block)
The A block is a polymer block containing a structural unit derived from a (meth) acrylic monomer. The structural unit derived from the (meth) acrylic monomer in the A block may have only one type or two or more types. By having a structural unit derived from the (meth) acrylic monomer, it is possible to maintain a high affinity with the dispersion medium (solvent) and the binder resin blended in the coloring composition.

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

The (meth) acrylic monomer is a (meth) acrylate having a chain alkyl group (linear alkyl group or branched alkyl group), a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having a polycyclic structure. , (Meta) acrylate having an aromatic group, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone-modified hydroxy group, (meth) having an alkoxy group. Examples thereof include acrylate, (meth) acrylate having an oxygen-containing heterocyclic group, (meth) acrylate having an acidic group, (meth) acrylic acid, and the like, and one or a combination of two or more of these can be used. Can be done.

As the (meth) acrylate having a linear alkyl group, a (meth) acrylate having a linear alkyl group having 1 to 20 carbon atoms is preferable, and the linear alkyl group has 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, and n-hexyl (meth) acrylate. Examples thereof 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 chain alkyl group, a (meth) acrylate having a branched chain alkyl group having 3 to 20 carbon atoms is preferable, and the branched chain alkyl group has 3 to 20 carbon atoms. 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, and 2-. Examples thereof 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 in the cyclic alkyl group. Examples of the cyclic alkyl group include a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group). Specific examples of the (meth) acrylate having a cyclic alkyl group having a monocyclic structure include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate and the like.

The (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure having 6 to 12 carbon atoms. Examples of the polycyclic structure include a cyclic alkyl group having a bridged ring structure (for example, an adamantyl group, a norbornyl group, and an isobornyl group). Specific examples of the (meth) acrylate having a polycyclic structure include isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and 2-methyl-2-adamantyl. Examples thereof include (meth) acrylate and 2-ethyl-2-adamantyl (meth) acrylate.

The (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms in the aromatic group. Examples of the aromatic group include an aryl group and the like, and may have a chain portion such as an alkylaryl group, an aralkyl group, an aryloxyalkyl group and the like. Specific examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

Examples of the (meth) acrylate having the polyalkylene glycol structural unit include polyethylene glycol (polymerization degree = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree = 2 to 10) ethyl ether (meth) acrylate, and polyethylene. Polypropylene glycol (meth) acrylate having polyethylene glycol structural units such as glycol (polymerization degree = 2 to 10) propyl ether (meth) acrylate, polyethylene glycol (polymerization degree = 2 to 10) phenyl ether (meth) acrylate; polypropylene glycol (polymerization degree) = 2-10) Methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2-10) ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2-10) propyl ether (meth) acrylate, polypropylene glycol (polymerization) Degree = 2-10) Examples thereof include (meth) acrylate having a polypropylene glycol structural unit such as phenyl ether (meth) acrylate.

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, and 6-. Examples thereof include hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate. Among these, (meth) acrylate having a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable.

Examples of the (meth) acrylate having a lactone-modified hydroxy group include those in which a lactone is added to the (meth) acrylate having a hydroxy group, and those in which caprolactone is added are preferable. The amount of caprolactone added 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 a 1 mol addition of caprolactone of 2-hydroxyethyl (meth) acrylate, a 2 mol addition of caprolactone of 2-hydroxyethyl (meth) acrylate, and a 2-hydroxyethyl (meth) acrylate. 3 mol addition of caprolactone, 4 mol addition of caprolactone of 2-hydroxyethyl (meth) acrylate, 5 mol addition of caprolactone of 2-hydroxyethyl (meth) acrylate, 10 mol addition of caprolactone of 2-hydroxyethyl (meth) acrylate and the like are preferable. ..

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

As the (meth) acrylate having an oxygen-containing heterocyclic group, a (meth) acrylate having a 4-membered ring to 6-membered ring oxygen-containing heterocyclic group is preferable. 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 trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, Examples thereof include 1,3-dioxane- (meth) acrylate.

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 3 H 2). PO ₂ H ₂ ) can be mentioned. Examples of the (meth) acrylate having an acidic group include a (meth) acrylate having a carboxy group, a (meth) acrylate having a phosphoric acid group, and a (meth) acrylate having a sulfonic acid group.

Examples of the (meth) acrylate having a carboxy group include carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2-. Examples thereof include a monomer obtained by reacting a (meth) acrylate having a hydroxy group such as (meth) acryloyloxyethyl phthalate with an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride. Examples of the (meth) acrylate having a sulfonic acid group include ethyl sulfonate (meth) acrylate. Examples of the (meth) acrylate having a phosphoric acid group include 2- (phosphonooxy) ethyl (meth) acrylate.

The A block may have a structural unit other than the structural unit derived from the (meth) acrylic monomer. The other structural unit that can be contained in the A block is not particularly limited as long as it is formed of a vinyl monomer that can be copolymerized with both the (meth) acrylic monomer and the vinyl monomer that forms the B block described later. The vinyl monomer that can form 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 α-olefin, aromatic vinyl monomer, vinyl monomer containing a heterocycle, vinylamide, vinyl carboxylate, dienes and the like. These vinyl monomers may have a hydroxy group and 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 heterocyclic vinyl monomer include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, and N-benzyl. Maleimide, N-cyclohexylmaleimide and the like can be mentioned.
Examples of vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam and the like.
Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
Examples of the diene include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadien and the like.

The A block preferably contains a structural unit represented by the general formula (10), that is, a structural unit derived from the (meth) acrylate having a lactone-modified hydroxy group. Since the structural unit represented by the general formula (10) has an ester-bonded portion and a terminal hydroxy group in the side chain, it has a high affinity with a dispersion medium and a binder resin, and has alkali developability of a block copolymer. To increase.

［一般式（１０）において、ｎ１は１〜１０の整数を表す。Ｒ¹は水素原子またはメチル基を表す。Ｒ²は炭素数が１〜１０のアルキレン基を表す。Ｒ³は炭素数が１〜１０のアルキレン基を表す。］

[In the general formula (10), n1 represents an integer of 1 to 10. R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms. R ³ represents an alkylene group having 1 to 10 carbon atoms. ]

N1 in the above formula (10) is preferably an integer of 1 to 7, and more preferably an integer of 1 to 5.

The alkylene group having 1 to 10 carbon atoms represented by R ^{2 may be linear or branched, but linear is preferable.} Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ² include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Nonamethylene group, decamethylene group, 1-methylethylene group and the like can be mentioned. R ² is preferably an alkylene group having 1 to 5 carbon atoms.

The alkylene group having 1 to 10 carbon atoms represented by R ^{3 may be linear or branched, but linear is preferable.} Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ³ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Nonamethylene group, decamethylene group and the like can be mentioned. R ³ is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms.

When the A block contains a structural unit represented by the general formula (10), the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 20% by mass or more in 100% by mass of the A block. Is 30% by mass or more, particularly preferably 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. By setting the content of the structural unit derived from the (meth) acrylate having a lactone-modified hydroxy group within the above range, the alkali developability of the block copolymer can be enhanced.

The A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably (meth) acrylate having an acidic group, (meth) acrylic acid). Having a structural unit derived from a vinyl monomer having an acidic group increases the solubility in an alkaline developer and can improve the alkaline developability. However, if the ratio is large, the affinity with the solvent and the alkali-soluble resin may be lowered. Therefore, the proportion of the structural unit derived from the vinyl monomer having an acidic group is preferably such that the acid value of the entire 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 thereof is preferably 2% by mass or more, preferably 20% by mass or less in 100% by mass of A block. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with alkali is high in alkaline development, and if it is 20% by mass or less, the hydrophilicity is high. Not too much, and it is possible to prevent the formed pixels from becoming cluttered.

The content of the structural unit represented by the general formula (1) described later is less than 10% by mass, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1. Most preferably, it does not contain a mass% or less and a structural unit represented by the general formula (1). The lower the content of the structural unit represented by the general formula (1) in the A block, the better the dispersion performance of the coloring material.

The A block preferably has no 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. If a large amount of amino groups are present in the A block, the coloring material is adsorbed on both the A block and the B block when used as a dispersant, and the dispersion performance of the coloring material deteriorates. The content of the structural unit (including the quaternized amino group) derived from the vinyl monomer having an amino group in the A block is preferably 3% by mass or less, more preferably 1% by mass or less. It is more preferably 0.1% by mass or less, and most preferably 0% by mass.

When two or more kinds of 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. , It is preferable that it is contained in the form of random copolymerization from the viewpoint of uniformity. For example, the A block may be formed by a copolymer of a structural unit composed of a1 block and a structural unit composed of a2 block.

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

(Structural unit represented by the general formula (1))
The structural unit represented by the general formula (1) may have only one type or two or more types. By having the structural unit represented by the general formula (1), the adsorptivity with the coloring material is high, and the generation of formaldehyde over time can be suppressed. In the structural unit represented by the general formula (1), ^{−Y 1} −N—R ¹¹ R ¹² bonded to ^{X 1} is the structure represented by the general formula (5).

［一般式（１）において、Ｒ¹¹は、水素原子、置換基を有していてもよい炭素数２以上である鎖状もしくは環状の炭化水素基を表す。Ｒ¹²は、置換基を有していてもよい炭素数２以上である鎖状もしくは環状の炭化水素基を表す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｒ¹³は水素原子またはメチル基を表す。Ｘ¹はアミド基、エステル基、または、単結合を表す。Ｙ¹は２価の炭化水素基を表す。］

[In the general formula (1), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents an amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ]

^{R 11} and R ¹² in the general formula (1) are synonymous with ^{R 11} and R ¹² in the general formula (5). Examples of the chain hydrocarbon group and the cyclic hydrocarbon group represented by ^{R 11} and R ¹² in the general formula (1) include those exemplified by ^{R 11} and R ^{12 in the general formula (5). The linear alkyl group represented by R 11} and R ¹² in the general formula (1) preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 2 to 5 carbon atoms. Preferably, the branched alkyl group has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms.

Examples of the cyclic structure formed by bonding R ¹¹ and R ¹² to each other include a nitrogen-containing heterocycle having a 5-membered ring to a 7-membered ring or a fused ring formed by condensing two of them. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specific examples thereof include structures represented by the following formulas (1-1), (1-2), and (1-3).

［一般式（１−１）、（１−２）、（１−３）において、Ｒ¹⁴は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ¹⁴は、それぞれ同一でも異なっていてもよい。］

[In the general formulas (1-1), (1-2), and (1-3), R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * Represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, the plurality of R ^14s existing may be the same or different. ]

The X ¹ represents an amide group (-CO-NH-), an ester group (-CO-O-), or a single bond. The bonding direction of the amide group and the ester group is not particularly limited. Examples of the bonding mode of the amide group include C-CO-NH-Y ¹ and C-NH-CO-Y ¹ , and C-CO-NH-Y ¹ is preferable. Examples of the bonding mode of the ester group include C-CO-O-Y ¹ and C-O-CO-Y ¹ , and C-CO-O-Y ¹ is preferable.

^{Y 1} in the general formula (1) is synonymous with ^{Y 1} in the general formula (5). The Y ¹ is preferably an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear or branched, but linear is preferable. Y ¹ is preferably an alkylene group having 1 to 5 carbon atoms.

Specific examples of the vinyl monomer forming the structural unit represented by the general formula (1) include ethylaminoethyl (meth) acrylate, ethylaminopropyl (meth) acrylate, ethylaminobutyl (meth) acrylate, and diethylaminoethyl (meth). ) Acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, propylaminoethyl (meth) acrylate, propylaminopropyl (meth) acrylate, propylaminobutyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, Examples thereof include dipropylaminopropyl (meth) acrylate, dipropylaminobutyl (meth) acrylate, and tert-butylaminoethyl (meth) acrylate.

The content of the structural unit represented by the general formula (1) is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and 98% by mass in 100% by mass of the B block. % Or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. It is considered that the structural unit represented by the general formula (1) has a high affinity with the coloring material by setting the content in this range.

The B block may have a structural unit represented by the general formula (2). The structural unit represented by the general formula (2) in the B block may have only one type or two or more types. If the B block has a structural unit represented by the general formula (2), strong adsorptivity to the surface of the coloring material can be maintained for a long period of time, and storage stability is further improved.

［一般式（２）において、Ｒ²¹は、水素原子、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表す。Ｒ²²およびＲ²³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表す。Ｒ²²およびＲ²³が互いに結合して環状構造を形成していてもよい。Ｒ²⁴は水素原子またはメチル基を表す。Ｘ²はアミド基、エステル基、または、単結合を表す。Ｙ²は２価の炭化水素基を表す。］

[In the general formula (2), R ²¹ represents a chain or cyclic hydrocarbon group which may have a hydrogen atom and a substituent. R ²² and R ²³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ²² and R ²³ may be combined with each other to form an annular structure. R ²⁴ represents a hydrogen atom or a methyl group. X ² represents an amide group, an ester group, or a single bond. Y ² represents a divalent hydrocarbon group. ]

Examples of the chain hydrocarbon group represented by R ^{21 to} R ²³ include a linear alkyl group and a branched chain alkyl group. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, further preferably 2 to 10 carbon atoms, and particularly preferably 2 to 5 carbon atoms. Examples of the linear alkyl group include an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-nonyl group, an n-decyl group and an n-lauryl group. .. The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a neopentyl group, an isooctyl group and the like.

Examples of the substituent contained in the chain hydrocarbon group represented by R ^{21 to R 23} include a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H ₅ ), a hydroxy group and the like.

Examples of the cyclic hydrocarbon group represented by R ^{21 to} R ²³ include a cyclic alkyl group and an aromatic group, and the cyclic alkyl group and the aromatic group may have a chain portion. The cyclic alkyl group preferably has 4 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of the cyclic alkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. The aromatic group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 6 to 8 carbon atoms. Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, a mesitylene group and the like. Examples of the chain portion of the cyclic alkyl group having a chain portion and the aromatic group having a chain portion include an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably carbon. The number 1 to 3 alkylene groups can be mentioned.

Examples of the substituent contained in the cyclic hydrocarbon group represented by R ^{21 to R 23} include a halogen group, an alkoxy group, a chain alkyl group, a hydroxy group and the like.

Examples of the cyclic structure formed by bonding R ²² and R ²³ with each other include a nitrogen-containing heterocycle having a 5-membered ring to a 7-membered ring or a fused ring formed by condensing two of them. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specific examples thereof include structures represented by the following equations (2-1), (2-2), and (2-3).

［一般式（２−１）、（２−２）、（２−３）において、Ｒ²⁵は、Ｒ²¹である。Ｒ²⁶は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ²⁶は、それぞれ同一でも異なっていてもよい。］

[In the general formulas (2-1), (2-2), and (2-3), R ²⁵ is R ²¹ . R ²⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer from 0 to 5. m represents an integer from 0 to 4. n represents an integer from 0 to 4. * Represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ^26s may be the same or different. ]

The X ² represents an amide group (-CO-NH-), an ester group (-CO-O-), or a single bond. The bonding direction of the amide group and the ester group is not particularly limited. Examples of the bonding mode of the amide group include C-CO-NH-Y ² and C-NH-CO-Y ² , and C-CO-NH-Y ² is preferable. Examples of the bonding mode of the ester group include C-CO-O-Y ² and C-O-CO-Y ² , and C-CO-O-Y ² is preferable.

Examples of the divalent hydrocarbon group represented by Y ² include an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, and an arenediyl group having 6 to 10 carbon atoms. Among these, an alkylene group having 1 to 10 carbon atoms is preferable. The alkylene group may be linear or branched, but linear is preferable. Y ² is preferably an alkylene group having 1 to 5 carbon atoms.

Z ^- The halogen anion, carboxylate anion, sulfate anion, sulfonate anion, phosphate anion, and the like nitroxide anion.
Examples of the halogen anion include a fluoro anion, a chloro anion, a bromo anion, and an iodine anion.
Examples of the carboxylate anion include alkyl carboxylate anions such as acetate anion and propionic acid anion; and aromatic carboxylate anions such as benzoate anion.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkyl sulfonate anions such as methanesulfonic acid anion and ethanesulfonic acid anion; and aromatic sulfonate anions such as benzenesulfonic acid anion and toluenesulfonic acid anion.
Examples of the phosphate anion include alkyl phosphate anions such as methylphosphonic acid anion and ethylphosphonic acid anion; and aromatic phosphate anions such as phenylphosphonic acid anion and benzylphosphonic acid anion.

Specific examples of the vinyl monomer forming the structural unit represented by the formula (2) include (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxypropylbenzyldiethylammonium chloride, and (meth) acryloyloxybutylbenzyl. Diethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethylammonium bromide, (meth) acryloyloxybutylbenzyldiethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium iodide, (meth) Meta) Acryloyloxypropylbenzyl diethylammonium iodide, (meth) acryloyloxybutylbenzyldiethylammonium iodide, (meth) acryloyloxyethylbenzyldiethylammonium fluoride, (meth) acryloyloxypropylbenzyldiethylammonium fluoride, (meth) Examples thereof include acryloyloxybutylbenzyldiethylammonium fluoride.

When the structural unit represented by the general formula (2) is contained, the content is preferably 2% by mass or more, more preferably 20% by mass or more, and 90% by mass or less in 100% by mass of the B block. It is preferably, more preferably 70% by mass or less. It is considered that the structural unit represented by the general formula (2) has a high affinity with the coloring material by setting the content in this range.

The B block may be only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may include other structural units. From the viewpoint of maintaining the 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 (2) in the B block is 100 mass by mass of the B block. In%, it is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. Further, it is preferable that the B block substantially does not 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 in 100% by mass of the B block.

Specific examples of the vinyl monomer capable of forming other structural units of the B block include the same as those exemplified as specific examples of the vinyl monomer capable of forming other structural units of the A block.

When two or more kinds of structural units are contained in the B block, the 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. , It is preferable that it is contained in the form of random copolymerization from the viewpoint of uniformity. For example, the B block may be formed by a copolymer of a structural unit composed of b1 blocks and a structural unit composed of b2 blocks.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. 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, the A block is A and the B block is B. when expressed as, (a-B) _m type, (a-B) _m -A type, the group consisting of (B-a) _m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) It is preferable that the copolymer has at least one structure selected from the above. Among these, AB type diblock copolymers are preferable from the viewpoint of handleability during processing and physical properties of the composition. By constructing the AB type diblock copolymer, the structural unit derived from the (meth) acrylic monomer contained in the A block and the structural unit represented by the general formula (1) contained in the B block are localized. It is considered that the colorant can be efficiently acted on the dispersion medium (solvent) and the binder resin (alkali-soluble resin). The block copolymer may have blocks other than the A block and the B block.

The content of A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 85% by mass or less in 100% by mass of the entire block copolymer. It is more preferably 80% by mass or less, still more preferably 75% by mass or less. The content of B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 65% by mass or less in 100% by mass of the entire block copolymer. It is more preferably 60% by mass or less, still more preferably 55% by mass or less. By adjusting the content of A block and B block within the above range, the dispersion performance when used as a dispersant is further improved.

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

When the block copolymer contains a structural unit having an acidic group, the content of the structural unit derived from the vinyl monomer having an acidic group in the block copolymer is preferably 1% by mass or more, preferably 10% by mass or less. Is preferable.

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

The molecular weight of the block copolymer is measured by a gel permeation chromatography (hereinafter referred to as "GPC") method. 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, 40, It is preferably 000 or less, more preferably 30,000 or less, still more preferably 25,000 or less, and particularly preferably 20,000 or less. When the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.

The molecular weight distribution (PDI) of the block copolymer is preferably 2.5 or less, more preferably 2.0 or less, still 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 copolymer has a uniform molecular weight. When the value is 1.0, the width of the molecular weight distribution is the narrowest. That is, the lower limit of PDI is 1.0. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.5, 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 50 mgKOH / g or more, still more preferably 80 mgKOH / g or more, from the viewpoint of adsorptivity to the coloring material and dispersibility of the coloring material. It is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less.

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, and preferably 50 mgKOH / g or less. By setting the acid value in this range, it is possible to preferably act with the binder resin (alkali-soluble resin) without impairing the affinity of the block copolymer with the coloring material.

(Manufacturing method of block copolymer)
As a method for producing the block copolymer, a method in which the A block is first produced and the B block monomer is polymerized in the A block by the polymerization reaction of the vinyl monomer; the B block is produced first and the B block is A. A method of polymerizing block monomers; a method of separately producing the A block and the B block and then coupling the A block and the B block can be mentioned.

The polymerization method is not particularly limited, but living radical polymerization is preferable. That is, as the block copolymer, one polymerized by living radical polymerization is preferable. In the conventional radical polymerization method, inactivation of the growth end occurs not only by the start reaction and the growth reaction but also by the termination reaction and the chain transfer reaction, and there is a tendency that a mixture of polymers having various molecular weights and a non-uniform composition tends to be obtained. On the other hand, the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, but is less likely to cause a termination reaction or chain transfer, and grows without deactivating the growth end. It is preferable because it is easy to precisely control and produce a polymer having a uniform composition.

The living radical polymerization method includes a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); and an organotellurium compound, depending on the method for stabilizing the polymerization growth end. There are methods such as the method used (TERP method). Since the ATRP method uses an amine complex, it may not be possible to use the vinyl monomer having an acidic group without protecting the acidic group. In the RAFT method, when various monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be problems such as sulfur odor and coloring. Among these methods, it is preferable to use the TERP method from the viewpoint of the variety of monomers that can be used, the control of the molecular weight in the polymer region, the uniform composition, or the coloring.

The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. For example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. It is the method described in 2004/072126 and 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) The vinyl monomer is polymerized using the organic tellurium compound represented by the general formula (3).
(B) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3) and an azo-based polymerization initiator.
(C) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3) and an organic diterlide compound represented by the general formula (4).
(D) The vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (3), an azo-based polymerization initiator and an organic diterlide compound represented by the general formula (4).

［一般式（３）において、Ｒ³¹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。Ｒ³²およびＲ³³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。Ｒ³⁴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（４）において、Ｒ³¹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 (3), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R ³² and R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In the general formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

The ^{group represented by R 31} is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and is specifically as follows.
Alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and heptyl. Examples thereof include a linear or branched alkyl group such as a group and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a linear or branched 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 frill group, a thienyl group and the like.

The ^{groups represented by R 32} and R ³³ are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and each group is specifically as follows.
Alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and heptyl. Examples thereof include a linear or branched alkyl group such as a group and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

The ^{group represented by R 34} is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a group. It is a propargyl group, and the specifics are as follows.
Alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and heptyl. Examples thereof include a linear or branched alkyl group such as a group and an octyl group, and a cyclic alkyl group such as a cyclohexyl group. It is preferably a linear or branched 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. It is preferably 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 the substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by ^{−COR 341 (R 341} is carbon). Alkyl group (1 to 8), aryl group, alkoxy group or aryloxy group having 1 to 8 carbon atoms), sulfonyl group, trifluoromethyl group and the like can be mentioned. Further, these substituents are preferably substituted by one or two.
Examples of the aromatic heterocyclic group include a pyridyl group, a frill group, a thienyl group and the like.
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, and for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert- Examples thereof include a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like.
Examples of the acyl group include an acetyl group, a propionyl group, a benzoyl group and the like.
Examples of the amide group include −CONR ³⁴²¹ R ³⁴²² (R ³⁴²¹ and R ³⁴²² are independently hydrogen atoms and alkyl or aryl groups having 1 to 8 carbon atoms, respectively).
As the oxycarbonyl group, a group represented by −COOR ³⁴³¹ (R ³⁴³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable, and for example, a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl is preferable. Examples thereof include a group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, a phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include a methoxycarbonyl group and an ethoxycarbonyl group.
As the aryl group, −CR ³⁴⁴¹ R ³⁴⁴² −CR ³⁴⁴³ = CR ³⁴⁴⁴ R ³⁴⁴⁵ (R ³⁴⁴¹ and R ³⁴⁴² are independently hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, R ³⁴⁴³ , R ³⁴⁴⁴ and R ³⁴⁴⁵ are each independently. , Each independently has a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and each substituent may be connected by a cyclic structure).
As the propargyl group, −CR ³⁴⁵¹ R ³⁴⁵² −C≡CR ³⁴⁵³ (R ³⁴⁵¹ and R ³⁴⁵² are hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, ^{and R 3453 is hydrogen atoms or alkyl groups having 1 to 8 carbon atoms.} , Aryl group or silyl group) and the like.

Specific examples of the organic tellurium compound represented by the general formula (3) are (methylteranylmethyl) benzene, (methylteranylmethyl) naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, and ethyl-2-. Methyl-2-n-butylteranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylteranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylteranyl-propionate or (3-trimethylsilylpropargyl) ) -2-Methyl-2-methylteranyl-propionate, etc., Organics described in International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication No. 2004/072126, and International Publication No. 2004/096870. All of the tellurium compounds can be exemplified.

Specific examples of the organic diterlide compound represented by the general formula (4) include dimethyl diterlide, diethyl diterlide, di-n-propyl diterlide, diisopropyl diterlide, dicyclopropyl diterlide, and di. -N-butyl diterlide, di-s-butyl diterlide, di-t-butyl diterlide, dicyclobutyl diterlide, diphenyl diterlide, bis- (p-methoxyphenyl) diterlide, bis- (p-aminophenyl) diterlide, bis Examples thereof include − (p-nitrophenyl) diterlide, bis- (p-cyanophenyl) diterlide, bis- (p-sulfonylphenyl) diterlide, dinaphthyl diterlide, dipyridyl diterlide 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-cyanovalerian 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) propane], 2 , 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2 , 2'-Azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) and the like can be exemplified.

The polymerization step is a container substituted with an inert gas, and the vinyl monomer and the organic tellurium compound of the general formula (3) are further azo for the purpose of promoting the reaction according to the type of the vinyl monomer, controlling the molecular weight and the molecular weight distribution, and the like. The system polymerization initiator and / or the organic diterlide compound of the general formula (4) are mixed. At this time, examples of the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferable.

The amount of the vinyl monomer used in the above (a), (b), (c) and (d) may be appropriately adjusted according to the physical characteristics of the target copolymer. It is preferable that the vinyl monomer is 5 mol to 10000 mol with respect to 1 mol of the organic tellurium compound of the general formula (3).

When the organic tellurium compound of the general formula (3) of the above (b) and the azo-based polymerization initiator are used in combination, 0.01 mol to 10 mol of the azo-based polymerization initiator is added to 1 mol of the organic tellurium compound of the general formula (3). Is preferable.

When the organic tellurium compound of the general formula (3) and the organic diterlide compound of the general formula (4) are used in combination, the organic of the general formula (4) is compared with 1 mol of the organic tellurium compound of the general formula (3). The diterlide compound is preferably 0.01 mol to 100 mol.

When the organic telluryl compound of the general formula (3) of the general formula (d), the organic diterlide compound of the general formula (4) and the azo-based polymerization initiator are used in combination, it is generally compared with 1 mol of the organic tellurium compound of the general formula (3). The organic diterlide compound of the formula (4) is preferably 0.01 mol to 100 mol, and the azo-based polymerization initiator is preferably 0.01 mol to 10 mol with respect to 1 mol of the organic telluryl compound of the general formula (3).

The polymerization reaction can be carried out without a solvent, but the mixture may be carried out by stirring using an aprotic solvent or a protic solvent generally used in radical polymerization. Aprotonic solvents that can be used 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, chloroform. , Carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like can be exemplified. Examples of the protonic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol and the like.

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

The reaction temperature and reaction time may be appropriately adjusted according to the molecular weight or molecular weight distribution of the obtained copolymer, but 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 normal pressure, but pressurization or depressurization may be performed.

After completion of the polymerization reaction, the solvent used, the residual vinyl monomer, and the like can be removed from the obtained reaction mixture by ordinary separation and purification means to separate the desired copolymer.

The growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR ³¹ derived from the tellurium compound (R ³¹ is the same as above in the formula), and is inactivated by an operation in air after the completion of the polymerization reaction. However, tellurium atoms may remain. It is preferable to remove the tellurium atom because the copolymer in which the tellurium atom remains at the terminal is colored or has poor thermal stability.

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

The other end of the copolymer obtained by the polymerization reaction (the end opposite to the growth end) is -CR ³² R ³³ R ³⁴ derived from the tellurium compound (in the formula, R ³² , R ³³ and R ³⁴ are of the formula. (3) It is the same ^{as R 32} , R ³³ and R ^{34 in).}

When the tertiary amine group of the structural unit represented by the formula (1) is quaternized, the quaternizing agent includes alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; benzyl chloride. , Haloalkane aralkyl such as benzyl bromide and benzyl iodide; dimethyl sulfate; dialkyl sulfate such as diethyl sulfate and di-n-propul sulfate. Among these, benzyl chloride, benzyl bromide, benzyl iodide and the like are preferably halogenated aralkyl, and more preferably benzyl chloride. An alkyl group and an aralkyl group derived from the quaternizing agent are introduced into the structure after quaternization. Therefore, the amount of the structural unit represented by the formula (2) can be estimated by measuring the amount of the alkyl group and the aralkyl group introduced by the quaternization.

Examples of the method for quaternizing a part of the tertiary amine structure of the structural unit represented by the formula (1) in the polymer include a method of contacting the polymer with a quaternizing agent. Specifically, a method of polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (1), adding a quaternizing agent to the reaction solution, and stirring the reaction solution can be mentioned. .. The temperature of the reaction solution to which the quaternizing agent is added is preferably 55 ° C. to 65 ° C., and the stirring time is preferably 5 hours to 20 hours. When adding the quaternizing agent, it is also preferable to dilute the reaction solution after the polymerization. Examples of the solvent added for dilution include a solvent that can be used in the polymerization reaction, and a protonic solvent is preferable, and methanol is more preferable.

(Polymerization product)
As the dispersant composition, a polymerization product containing the block copolymer may be used as the dispersant component. The polymerization product refers to a product obtained when a polymerization operation (quarterization treatment if necessary) is performed to obtain the block copolymer. The polymerization product contains a desired block copolymer and polymer impurities produced as a by-product when synthesizing the block copolymer.

The polymer impurities are other polymers that are inevitably by-produced when synthesizing a desired block copolymer. For example, examples of the polymer impurities produced as a by-product when synthesizing the AB diblock copolymer include a random polymer having the same composition as the A block and a random polymer having the same composition as the B block. The polymer impurity is a polymer produced as a by-product when synthesizing a desired block copolymer, and does not include a polymer to be added separately.

The content of the block copolymer in the polymerization product is preferably 50% by mass or more based on 100% by mass of the polymerization product. When the content of the block copolymer in the polymerization product is 50% by mass or more, the dispersion performance is improved when the polymerization product is used as a dispersant.

(Distributed medium)
The dispersant composition may contain a dispersion medium. As the dispersion medium, as long as the block copolymer is dispersed or dissolved, does not react with these components, and has appropriate volatility, it can be appropriately selected and used. For example, conventionally known organic solvents can be used, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene. Glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, methoxypropanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and other glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, Propropylene 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 monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and other glycol alkyl ether acetates. G: Glycoldiacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate; Alkyl acetates such as cyclohexanol acetate; Amyl ether, propyl ether, diethyl ether, Ethers such as dipropyl ether, diisopropyl ether, butyl ether, diamil ether, ethyl isobutyl ether, dihexyl ether; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, Ketones such as cyclohexanone, ethylamyl ketone, methylbutyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, di Monovalent or polyhydric alcohols such as propylene glycol, triethylene glycol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane. Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene and cumene; amylformate, ethylformate, ethyl acetate, butyl acetate, acetic acid Propyl, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprilate, butyl stearate, ethyl benzoate, 3-ethoxypropionic acid Chain or cyclic esters such as methyl, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3 − Alkoxycarboxylic acids such as methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amilk loride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile. and others Is done.

The content of the dispersion medium in the dispersant composition is not particularly limited and can be adjusted as appropriate. The upper limit of the content of the dispersion medium in the dispersant composition is usually 99% by mass. The lower limit of the content of the dispersion medium in the dispersant composition is usually 10% by mass, preferably 30% by mass, in consideration of the viscosity suitable for producing the coloring composition described later.

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

(Coloring material)
The type of the coloring material may be appropriately selected according to the intended use, and examples thereof include pigments and dyes. The coloring composition preferably contains a pigment as a coloring material from the viewpoint of light resistance and heat resistance. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable. Examples of the pigment include pigments of each color such as red pigment, yellow pigment, orange pigment, blue pigment, green pigment, and purple pigment. The structure of the pigment is as follows: azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindolin pigments, quinacridone pigments, indigo. Examples thereof include polycyclic pigments such as system pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The pigment contained in the coloring composition may be only one type or may be a plurality of types.

Specific examples of pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 166, 168, Red pigments such as 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264, 269; C.I. 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. Pigment Orange 36, 38, 43 and other orange pigments; C.I. I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and other blue pigments; C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, Aluminum Phthalocyanine, Polyhalide Aluminum Phthalocyanine, Aluminum Phthalocyanine Hydroxide, Diphenoxyphosphinyloxyaluminum Phthalocyanine, Diphenylphosphinyloxyaluminum Phthalocyanine, Polyhalogenated Diphenoxy Green pigments such as phosphinyloxyaluminum phthalocyanine, polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; I. Examples thereof include purple pigments such as Pigment Violet 23, 32, and 50. Among these, pigments are 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 the coloring composition of the present invention is used to form a light-shielding material such as a black matrix of a color filter, 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, titanium black and the like. Among these, carbon black and titanium black are preferable from the viewpoint of shading rate and image characteristics.

The average particle size of the coloring material may be appropriately selected depending on the intended use, and is not particularly limited. From the viewpoint of high transparency and high contrast, the coloring composition preferably contains a coloring material having an average particle size of 10 nm to 150 nm.

The coloring material may contain a dye derivative as a dispersion aid. The dye derivative preferably contains an acidic dye derivative having an acidic group in order to ionic bond with the amino group in the polymer contained in the dispersant composition and adsorb it. This dye derivative has an acidic functional group introduced into the dye skeleton. As the pigment skeleton, a skeleton that is the same as or similar to the coloring material constituting the coloring composition, and a skeleton that is the same as or similar to the compound that is the raw material of the pigment are preferable. Specific examples of the pigment skeleton include an azo pigment skeleton, a phthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a triazine pigment skeleton, an acridine pigment skeleton, and a perylene pigment skeleton. As the acidic group introduced into the dye skeleton, a carboxy group, a phosphoric acid group and a sulfonic acid group are preferable. A sulfonic acid group is preferable for the convenience of synthesis and the strength of 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 4 parts by mass to 17 parts by mass with respect to 100 parts by mass of the coloring material.

From the viewpoint of brightness, the upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and preferably 60% by mass in the total solid content of the coloring composition. Is more preferable. 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 later.

The content of the dispersant component (block copolymer and polymerization product) with respect to the coloring material in the coloring composition is preferably 5 parts by mass to 200 parts by mass, and 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the coloring material. It is preferably 100 parts by mass, and more preferably 10 to 80 parts by mass.

(Binder resin)
The coloring composition contains a binder resin (however, the polymer having a structure represented by the general formula (5) in the side chain is excluded). As a result, the alkali developability of the coloring composition and the binding property to the substrate can be enhanced. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group.

As the binder resin, a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from (meth) acrylate is preferable. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. Examples of the (meth) acrylate include methyl (meth) acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate.

The binder resin preferably has a total content of a structural unit derived from a carboxy group-containing vinyl monomer and a structural unit derived from (meth) acrylate of 50% by mass or more, more preferably 60% by mass or more, still more preferably. It is 70% by mass or more. The binder resin has a structure derived from a carboxy group-containing vinyl monomer having a content of 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 90% by mass or less. Is preferable, 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, and (meth). ) Random copolymers of acrylic acid, butyl (meth) acrylate and benzyl (meth) acrylate can be mentioned. 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 the carboxy group-containing vinyl monomer and the (meth) acrylate, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass and 10% by mass to 70% by mass in the total monomer components. It is preferably 20% by mass to 70% by mass, and more preferably 20% by mass to 70% by mass.

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

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

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

The binder resin contained in the coloring composition may be of only one type or may be of a plurality of types. In the coloring composition, the content of the binder resin is preferably 3 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass, and 20 parts by mass with respect to 100 parts by mass of the coloring material. It is more preferably parts to 80 parts by mass.

(Crosslinking agent)
The coloring composition may contain a cross-linking agent, if necessary. The cross-linking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an N-alkoxymethylamino group and the like. As the cross-linking agent, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

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 a (meth) acrylic acid, and a caprolactone-modified polyfunctional (? Meta) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate with hydroxy group with polyfunctional isocyanate, (meth) acrylate with hydroxy group Examples thereof include a polyfunctional (meth) acrylate having a carboxy group obtained by reacting 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 valents such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Aliphatic polyhydroxy compounds can be mentioned. Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Examples thereof include pentaerythritol hexa (meth) acrylate and glycerol di (meth) acrylate. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutacon anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; pyromellitic anhydride and biphenyltetracarboxylic acid. Examples thereof include tetrabasic acid dianhydrides such as acid dianhydrides and benzophenone tetracarboxylic acid dianhydrides.

In the coloring composition, the content of the cross-linking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the coloring material. If the content of the cross-linking 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 coloring composition of the present invention has a reduced alkali developability, and there is a tendency that background stains, film residues, etc. are likely to occur on the substrate or the light-shielding layer of the unexposed portion. ..

(Photopolymerization initiator)
The coloring composition may contain a photopolymerization initiator, if necessary. Thereby, the coloring composition can be imparted with radiation sensitivity. The photopolymerization initiator is a compound that generates an active species capable of initiating the polymerization of a cross-linking agent by exposure to radiation such as visible light, ultraviolet rays, far infrared rays, electron beams, and X-rays.

Examples of the photopolymerization initiator include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, onium salt-based compounds, benzoin-based compounds, benzophenone-based compounds, and α-diketones. Examples thereof include system compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, aminoketone compounds and the like. The photopolymerization initiator may be used alone or in combination of two or more.

In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 part by mass to 120 parts by mass, and particularly preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the cross-linking agent. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, while if it is too large, the formed colored layer tends to easily fall off from the substrate during development.

(Distributed medium)
The coloring composition contains a dispersion medium. As the dispersion medium, as long as it disperses or dissolves other components constituting the coloring composition, does not react with these components, and has appropriate volatility, it can be appropriately selected and used. For example, a conventionally known organic solvent can be used, and examples thereof include an organic solvent (dispersion medium) that can be used in the dispersant composition. The organic solvent is preferably glycol alkyl ether acetates, monohydric or polyhydric alcohols from the viewpoints of dispersibility of pigments and the like, solubility of dispersants, coatability of pigment dispersion compositions and the like. The solvent contained in the pigment dispersion composition may be only one type or may be a plurality of types.

When the pixels of the color filter are formed by the photolithography method, the boiling point of the dispersion medium (under the condition of pressure 1013.25 hPa. Hereinafter, the boiling points are all the same) is preferably 100 ° C. to 200 ° C. Among the above dispersion media, glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the coloring composition is relatively high. It is also preferable to use a dispersion medium having a boiling point of 150 ° C. or higher. By using a dispersion medium having a high boiling point, it is possible to suppress the destruction of the mutual relationship of the coloring composition due to the rapid drying of the coloring composition. The dispersion medium having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates. The content ratio of the dispersion medium having a boiling point of 150 ° C. or higher is preferably 3 to 50% by mass based on 100% by mass of the entire dispersion medium.

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

(Other compounding agents)
In addition to the above-mentioned compounding agent, other compounding agents may be blended in the coloring composition as long as the preferable physical properties of the present invention are not impaired. Other compounding agents include sensitizers, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, plasticizers, organic carboxylic acid compounds, and organic carboxylic acids. Acid anhydrides, pH adjusters, antioxidants, UV absorbers, light stabilizers, preservatives, antifungal agents, surfactants, anti-aggregation agents, adhesion improvers, development improvers, storage stabilizers, etc. be able to.

Examples of the sensitizing dye include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3 , 4-Diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2-( p-Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p) -Diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiaidazole, ( p-Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. Can be mentioned.

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

Examples of the nonionic surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a polyoxyethylene-based surfactant.
Anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulphates, alkyl sulphates, higher alcohol sulphates, aliphatics. Alcohol Sulfate Esters, Polyoxyethylene Alkyl Ether Sulfates, Polyoxyethylene Alkylphenyl Ether Sulfates, Alkyl Phosphate Esters, Polyoxyethylene Alkyl Ether Phosphates, Polyoxyethylene Alkylphenyl Ether Phosphates, Special Polymer Surfactants Agents and the like can be mentioned.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like.
Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids and the like.

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

Examples of the organic carboxylic acid compound include monocarboxylic acids, carboxylic acids in which a carboxy group is directly bonded to a phenyl group, and carboxylic acids in which a carboxy group is bonded from a phenyl group via a carbon bond.

Organic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutacon anhydride, 1,2-anhydride. Cyclohexene dicarboxylic acid, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride and the like can be mentioned.

<Manufacturing method of coloring composition>
The coloring composition can be prepared by mixing a coloring material, a dispersant composition, a binder resin, a dispersion medium, and if necessary, a cross-linking agent, a photopolymerization initiator, and other compounding agents. 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. The coloring composition is preferably filtered after mixing. Since the coloring composition has alkali developability, it can be suitably used for a color filter.

Further, as the coloring material, one which has been surface-treated in advance with the dispersant composition of the present invention can also be used. As the surface treatment method, a dry method in which a dispersant is added and mixed while stirring the coloring material using a Henschel mixer, a ball mill, an atomizer colloid mill, a Bambari mixer, etc., or a wet method in which the solvent is removed after treatment in a solvent. Can be used. By performing the surface treatment with the dispersant composition of the present invention in this way, the dispersibility of the coloring material can be improved and aggregation can be prevented.

<Color filter>
The color filter of the present invention includes a colored layer formed by using the coloring composition.

Examples of the method for manufacturing the color filter include the following methods. First, thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin, and polymethylmethacrylate resin; thermocurable resin sheets such as epoxy resin, unsaturated polyester resin, and poly (meth) acrylic resin; various glasses, etc. The transparent substrate is provided with color pixels that transmit light of the three primary colors of red (R), green (G), and blue (B), and preferably includes a black matrix formed from the coloring composition. Is. As a method for producing a color filter, after applying a black coloring composition, prebaking is performed to evaporate a solvent (dispersion medium) to form a coating film. Next, the coating film is exposed to a photomask and then developed with an alkaline developer (an aqueous solution containing an organic solvent or a surfactant and an alkaline compound, etc.) to dissolve and remove the unexposed portion of the coating film. And form a black pattern (black matrix). Then, after post-baking as necessary, the same operation is repeated sequentially for red (R), green (G), and blue (B), so that the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate. The resulting color filter is obtained. However, in the present invention, the order in which the pixels of each color are formed is not limited to the above.

When the coloring composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a rotary coating method (spin coating method), a slit die coating method, or a bar coating method can be adopted. In particular, it is preferable to adopt the spin coating method and the slit die coating method.

A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film (indium tin oxide (ITO) or the like) is formed by sputtering. After forming 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 element, a color image pickup tube element, a color sensor, an organic EL display element, electronic paper, and the like.

Further, since the coloring composition has a low viscosity and excellent dispersibility of the coloring material, it is suitable as a coloring column spacer supported on a thin film transistor (TFT) substrate and a color filter substrate located with a liquid crystal layer sandwiched between them. Can be used for. For example, a composition having a high optical density (OD) described in Japanese Patent Application Laid-Open No. 2015-191234 can be mentioned.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof. The polymerization rate of the block copolymer and the binder resin, the weight average molecular weight (Mw), the molecular weight distribution (PDI) and the amine value, the formaldehyde amount of the dispersant composition, and the dispersibility (viscosity, particle size) of the coloring composition. Was evaluated according to the following method.

The meanings of the abbreviations are as follows.
BMA: Butyl methacrylate PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Co., Ltd., Praxel® FM5)
DMAEMA: Dimethylaminoethyl methacrylate DEAEMA: Diethylaminoethyl methacrylate TBAEMA: tert-Butylaminoethyl methacrylate BTEE: Ethyl-2-methyl-2-n-butylteranyl-propionate DBDT: Dibutylditerlide AIBN: 2,2'-azobis (iso) Butyronitrile)
PMA: Propylene glycol monomethyl ether acetate

(Polymerization rate)
¹ H-NMR was measured (solvent: CDCl ₃ , internal standard: TMS) using a nuclear magnetic resonance (NMR) measuring device (manufactured by Bruker Biospin, model: AVANCE500 (frequency 500 MHz)). With respect to the obtained NMR spectrum, the integral ratio of the peaks of the vinyl group derived from the monomer and the ester side chain derived from the polymer was obtained, 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, model HLC-8320). The column is one SHODEX KF-603 (φ6 mm × 150 mm) (manufactured by SHODEX), 10 mmol / L lithium bromide / 10 mmol / L acetic acid / N-methyl-2-pyrrolidone solution in the mobile phase, and a differential refractometer in the detector. It was used. The measurement conditions were a column temperature of 40 ° C., a sample concentration of 20 mg / mL, a sample injection amount of 10 μm, and a flow rate of 0.2 mL / min. A calibration curve (calibration curve) was prepared using polystyrene (molecular weight 427,000, 190,000, 96,400, 37,400, 10,200, 2,630,906) as a standard substance, and the weight average molecular weight (molecular weight) (molecular weight). Mw) and the number average molecular weight (Mn) were measured. The molecular weight distribution (PDI = Mw / Mn) was calculated from this measured value.

(Amine value)
The amine value represents the mass of the basic component and the equivalent amount of potassium hydroxide (KOH) per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized and titrated with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
B = 56.11 × Vs × 0.1 × f / w
B: Amine value (mgKOH / g)
Vs: Amount of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration (mL)
f: Titer of 0.1 mol / L hydrochloric acid (2-propanol property) w: Mass (g) of measurement sample (in terms of solid content)

(viscosity)
The viscosity was measured using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.) and a cone rotor (1 ° 34'x R24) at 25 ° C. and a rotor rotation speed of 60 rpm. The measurement was carried out on the colored composition which was stored at 25 ° C. for 2 hours after preparation.

(Particle size)
The particle size was measured at 25 ° C. using a concentrated particle size analyzer (trade name: FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement was carried out on the colored composition which was stored at 25 ° C. for 2 hours after the adjustment. Samples were diluted with propylene glycol monomethyl ether acetate (PGMEA) as needed.

(Amount of formaldehyde)
0.5 g of the dispersant composition was added to a cartridge filled with silica gel impregnated with DNPH (2,4-dinitrophenylhydrazine) (Waters, SepPak (registered trademark) DNPH silica plus cartridge (product number: WAT037500)). It was injected and allowed to stand at room temperature for 2 hours.
It was washed out with 4 mL of acetonitrile and made up to 5 mL. Liquid chromatograph (manufactured by Shimadzu Corporation, trade name: LC-10AD, column: Pro C18 RS (4.6 x 250 mm, 5 μm (manufactured by YMC)), mobile phase: acetonitrile / ultrapure water = 65:35 solution, column temperature : 40 ° C., flow velocity: 1.0 mL / min, detection wavelength: 360 nm), and use a two-kind aldehyde-DNPH mixed standard solution (0.1 μg aldehyde / μL acetonitrile, manufactured by Wako Pure Chemical Industries, Ltd.) as a standard substance for measurement. The amount of aldehyde was calculated from the measurement results.

<Manufacturing of block copolymer>
(Block Copolymer No. 1)
PCL5 (275.8 g), BMA (45.3 g), AIBN (1.64 g), PMA (80.3 g) were charged into a flask equipped with an argon gas introduction tube and a stirrer, and after argon replacement, BTEE (14. 99 g) and DBDT (18.47 g) were added, and the mixture was reacted at 60 ° C. for 7 hours. The polymerization rate was 98.3%.

A mixed solution of DEAEMA (191.4 g) and PMA (47.9 g) substituted with argon in advance was added to the obtained solution, and the mixture was reacted at 60 ° C. for 13.5 hours. The polymerization rate was 99.4%.

After completion of the reaction, the reaction solution was poured into stirring n-heptane. The precipitated polymer was suction-filtered and dried to obtain Block Copolymer No. I got 1. The obtained block copolymer No. In No. 1, Mw was 16,301, PDI was 1.44, and the amine value was 108 mgKOH / g. In addition, Table 2 shows the block copolymer No. The composition of 1 is shown. The content of each structural unit in the copolymer was calculated from the charging ratio and the polymerization rate of the monomers used in the polymerization reaction.

(Block Copolymer Nos. 2 and 3)
Block Copolymer No. Block Copolymer No. 1 was produced in the same manner as in Production Method 1. A few were made. Table 1 shows the monomers, organic tellurium compounds, organic diterlide compounds, azo-based polymerization initiators, solvents, reaction conditions, and polymerization rates used. Table 2 shows the composition, Mw, PDI, and amine value of each block copolymer. The content of each structural unit in the copolymer was calculated from the charging ratio and the polymerization rate of the monomers used in the polymerization reaction.

<Dispersant composition>
0.325 g of each block copolymer was dissolved in 0.675 g of PMA to prepare a dispersant composition. The amount of formaldehyde was measured for this dispersant composition and is shown in Table 2.

Dispersant Composition No. In No. 3, the B block of the block copolymer as a dispersant does not have the structural unit of the general formula (1), and the structural unit derived from dimethylaminoethyl methacrylate (in the general formula (1), R ¹¹ and R ¹² has a methyl group). This dispersant composition No. In No. 3, the amount of formaldehyde was as high as 1.7 ppm. On the other hand, the dispersant composition No. In Nos. 1 and 2, the B block of the block copolymer as a dispersant has the structural unit of the general formula (1). These dispersant compositions No. In Nos. 1 and 2, the amount of formaldehyde was 0.1 ppm and 0.0 ppm, which were significantly reduced.

<Synthesis of alkali-soluble resin (binder resin)>
A flask equipped with an argon gas introduction tube and a stirrer was charged with methacrylic acid (MAA) (40.0 g), benzyl methacrylate (BzMA) (160.0 g), and propylene glycol monomethyl ether acetate (PMA) (580.0 g). After substitution with argon, 2,2'-azobis (isobutyronitrile) (AIBN) (4.0 g), n-dodecanethiol (6.0 g) and PMA (20.0 g) were added and the temperature was raised to 90 ° C. While keeping the solution at 90 ° C., MAA (80.0 g), BzMA (320.0 g), AIBN (8.0 g), n-dodecanethiol (12.0 g), PMA (50.0 g) were added to the solution. It was added dropwise over 1.5 hours. 60 minutes after the completion of the dropping, the temperature was raised to 110 ° C., AIBN (0.8 g) and PMA (10.0 g) were added and reacted for 1 hour, and then AIBN (0.8 g) and PMA ( 10.0 g) was added and reacted for 1 hour, and AIBN (0.8 g) and PMA (10.0 g) were further added and reacted for 1 hour.

The obtained reaction solution was cooled to room temperature, PMA (240.0 g) was added, and a solution of an alkali-soluble resin having a non-volatile content of 39.5% was obtained. The alkali-soluble resin had a weight average molecular weight (Mw) of 9,150, a molecular weight distribution (PDI) of 1.92, and an acid value of 128 mgKOH / g.

<Preparation of coloring composition>
Coloring Composition No. 1
Pigment 8 parts by mass, block copolymer No. The compounding composition was adjusted to 16 parts by mass, 6 parts by mass of the alkali-soluble resin, and 80 parts by mass of PMA, and 555 parts by mass of 0.3 mm zirconia beads were added, and a bead mill (trade name: DISPERMAT CA, VMA-GETZMANN GmbH) was manufactured. ) Was mixed for 3 hours and sufficiently dispersed. After the dispersion was completed, the beads were filtered off to obtain a colored composition. For pigments, C.I. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) was used. The dispersibility of the obtained coloring composition was evaluated. The evaluation results are shown in Table 3.

Coloring Composition No. A few
Coloring composition No. except that the block copolymer was changed. In the same manner as in the preparation method of No. 1, the coloring composition No. A few were prepared. The evaluation results are shown in Table 3.

Coloring Composition No. All of Nos. 1 to 3 have good dispersibility of pigments. Therefore, it can be understood that the block copolymer in which the B block has the structural unit of the general formula (1) can be used as a dispersant. Further, in particular, the coloring composition No. 2 using a block copolymer in which the B block has a structural unit derived from diethylaminoethyl methacrylate. 1 is excellent in dispersibility of the pigment. Therefore, if a block copolymer having a structural unit derived from diethylaminoethyl methacrylate in the B block is used, the amount of formaldehyde can be reduced and a coloring composition having excellent pigment dispersibility can be obtained. Recognize.

The present invention includes the following embodiments.
(Embodiment 1)
A dispersant composition comprising a polymer having a structure represented by the general formula (5) in a side chain.
* -Y ^1- N-R ¹¹ R ¹² (5)
[In the general formula (5), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. Y ¹ represents a divalent hydrocarbon group. * Represents a bond. ]

(Embodiment 2)
The dispersant composition according to embodiment 1, wherein the amine value of the polymer is 10 mgKOH / g to 200 mgKOH / g.

(Embodiment 3)
In Embodiments 1 or 2, the polymer is a block copolymer having an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1). The dispersant composition according to the above.

［一般式（１）において、Ｒ¹¹は、水素原子、置換基を有していてもよい炭素数２以上である鎖状もしくは環状の炭化水素基を表す。Ｒ¹²は、置換基を有していてもよい炭素数２以上である鎖状もしくは環状の炭化水素基を表す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｒ¹³は水素原子またはメチル基を表す。Ｘ¹はアミド基、エステル基、または、単結合を表す。Ｙ¹は２価の炭化水素基を表す。］

[In the general formula (1), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents an amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ]

(Embodiment 4)
The dispersant composition according to Aspect 3, wherein the A block has a structural unit represented by the general formula (10).

［一般式（１０）において、ｎ１は１〜１０の整数を表す。Ｒ¹は水素原子またはメチル基を表す。Ｒ²は炭素数が１〜１０のアルキレン基を表す。Ｒ³は炭素数が１〜１０のアルキレン基を表す。］

[In the general formula (10), n1 represents an integer of 1 to 10. R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms. R ³ represents an alkylene group having 1 to 10 carbon atoms. ]

(Embodiment 5)
The dispersant composition according to Aspect 3 or 4, wherein the block copolymer has a molecular weight distribution (PDI) of 2.5 or less.

(Embodiment 6)
The dispersant composition according to any one of aspects 3 to 5, wherein the block copolymer is polymerized by living radical polymerization.

(Embodiment 7)
A coloring composition comprising the dispersant composition, coloring material, binder resin and dispersion medium according to any one of aspects 1 to 6.

(Embodiment 8)
The coloring composition according to aspect 7, which is for a color filter.

(Embodiment 9)
A color filter comprising a colored layer formed by using the coloring composition according to the eighth aspect.

Claims (9)

A dispersant composition comprising a polymer having a structure represented by the general formula (5) in a side chain.
* -Y ^1- N-R ¹¹ R ¹² (5)
[In the general formula (5), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. Y ¹ represents a divalent hydrocarbon group. * Represents a bond. ] The dispersant composition according to claim 1, wherein the amine value of the polymer is 10 mgKOH / g to 200 mgKOH / g. Claim 1 or 2 in which the polymer is a block copolymer having an A block having a structural unit derived from a (meth) acrylic monomer and a B block having a structural unit represented by the general formula (1). Dispersant composition according to.

[In the general formula (1), R ¹¹ represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a hydrogen atom and a substituent. R ¹² represents a chain or cyclic hydrocarbon group having 2 or more carbon atoms which may have a substituent. R ¹¹ and R ¹² may be coupled to each other to form an annular structure. R ¹³ represents a hydrogen atom or a methyl group. X ¹ represents an amide group, an ester group, or a single bond. Y ¹ represents a divalent hydrocarbon group. ] The dispersant composition according to claim 3, wherein the A block has a structural unit represented by the general formula (10).

[In the general formula (10), n1 represents an integer of 1 to 10. R ¹ represents a hydrogen atom or a methyl group. R ² represents an alkylene group having 1 to 10 carbon atoms. R ³ represents an alkylene group having 1 to 10 carbon atoms. ] The dispersant composition according to claim 3 or 4, wherein the block copolymer has a molecular weight distribution (PDI) of 2.5 or less. The dispersant composition according to any one of claims 3 to 5, wherein the block copolymer is polymerized by living radical polymerization. A coloring composition containing the dispersant composition, coloring material, binder resin and dispersion medium according to any one of claims 1 to 6. The coloring composition according to claim 7, which is for a color filter. A color filter comprising a colored layer formed by using the coloring composition according to claim 8.