JP2022177838A - Polymerization product containing block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization product which exhibits excellent storage stability and has excellent dispersion performance when used as a dispersant.

SOLUTION: The polymerization product contains a block copolymer having an A block with a structural unit derived from a (meth)acrylic vinyl monomer, and a B block with a structural unit represented by the general formula (1) in the figure. The polymerization product has a molecular weight distribution (PDI) less than or equal to 2.0, and a content of the block copolymer greater than or equal to 75 mass% based on 100 mass% of the polymerization product.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to polymerized products containing block copolymers and methods of making polymerized products.

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

In the manufacture of liquid crystal displays, after the pattern shape of the coloring material is formed, a transparent electrode for driving the liquid crystal is formed thereon by vapor deposition or sputtering, and an alignment film is further formed thereon for aligning the liquid crystal in a certain direction. formed. In order to obtain sufficient performance of these transparent electrodes and alignment films, their formation is generally carried out at a high temperature of 200° C. or higher. As the dispersant of the coloring composition, a resin-type dispersant is used because it is easy to design the structure. Heat resistance, such as a decrease in the heat resistance and a change in hue, becomes a problem. Therefore, in order to obtain a pigment dispersion composition that achieves both heat resistance and dispersibility, in Patent Document 1, from an A block having a quaternary ammonium base in a side chain and a B block having no quaternary ammonium base The use of an AB block copolymer as a pigment dispersant for color filters has been disclosed (see Patent Document 1 (claim 1, paragraphs 0049 to 0058)).

The coloring composition is required to have excellent properties such as vividness and high transparency, and the coloring material is made into fine particles. When the coloring material becomes fine particles, the surface energy increases, causing aggregation of the coloring material, resulting in poor storage stability and high viscosity of the coloring material dispersion. Therefore, in order to further improve the dispersibility of the coloring material, in Patent Document 2, an A block having a polyalkylene glycol chain in the side chain and a B block having a primary to tertiary amino group in the side chain (meta) Acrylic block copolymers have been disclosed (see Patent Document 2 (paragraphs 0039 to 0049)).

On the other hand, it is known to use a living polymerization method for the production of AB block copolymers (see, for example, Patent Document 3 (claim 1, page 20, lines 18-23)). Living polymerization methods include living anionic polymerization, living cationic polymerization, and living radical polymerization. Living anionic polymerization and living cationic polymerization require strict polymerization conditions, and the functional groups that can coexist are limited. However, the living radical polymerization method maintains the versatility of coexisting with polar functional groups and the simplicity of being unaffected by the purity of monomers and solvents, while maintaining precise control of molecular weight distribution and production of polymers with uniform composition. There is Therefore, a living radical polymerization method is used to produce a block copolymer having a narrow molecular weight distribution, a uniform composition, and having a polar group with a controlled molecular weight.

In addition, when a block copolymer is produced, it inevitably contains polymer impurities which are by-produced during polymerization. Therefore, methods for reducing the content of such polymer impurities have been proposed. For example, Patent Document 4 describes a purification method for selectively removing polymer impurities by liquid-liquid extraction using a specific solvent for a block copolymer after polymerization (Patent Document 4 ( See paragraphs 0017-0024)). However, Patent Document 4 discusses purification and removal of styrene homopolymers, but does not discuss methods for removing (meth)acrylic homopolymers.

JP 2012-068559 A JP 2014-167636 A WO2004/096870 JP 2015-113444 A

In recent years, as the properties required for coloring compositions have become more sophisticated, conventional dispersants have the problem that the viscosity and storage stability of the coloring composition are not sufficient. In addition, if the amount of dispersant used in order to improve the dispersibility of the coloring material is increased, heat resistance such as a decrease in the contrast ratio of the color filter and a change in hue will become a problem, so even a small amount has excellent dispersibility. There is a need for dispersants. However, when the block copolymer contains polymer impurities, the dispersibility and dispersion stability tend to deteriorate.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a block copolymer that can be used as, for example, a dispersant and has excellent dispersibility and dispersion stability, and a method for producing the same.

The polymerization product of the present invention that has been able to solve the above problems is a polymerization product obtained by polymerizing a monomer composition, and has a structural unit derived from a (meth)acrylic vinyl monomer. A block copolymer having a block and a B block having a structural unit represented by the following general formula (1), wherein the polymerization product has a molecular weight distribution (PDI) of 2.0 or less, and The content of the block copolymer is 75% by mass or more in 100% by mass of the polymerization product.

〔式（１）において、Ｒ¹¹およびＲ¹²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹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。Ｘ¹は２価の連結基を示す。Ｒ¹³は水素原子またはメチル基を示す。〕

[In formula (1), R ¹¹ and R ¹² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may combine with each other to form a cyclic structure. X ¹ represents a divalent linking group. ^R13 represents a hydrogen atom or a methyl group. ]

The polymerization product of the present invention contains a block copolymer having an A block having a structural unit derived from a (meth)acrylic vinyl monomer and a B block having a structural unit represented by general formula (1). do. This block copolymer has an A block and a B block, and thus has excellent dispersibility. Thus, the polymerized product of the invention can be used as a dispersant. Moreover, the content of the block copolymer in the polymerization product of the present invention is 75% by mass or more. In other words, the content of polymer impurities, such as a polymer consisting only of A blocks and a polymer consisting only of B blocks, is 25 mass % or less. Therefore, the polymerized product of the present invention exhibits excellent storage stability when used as a dispersant.

The method for producing a polymerization product of the present invention includes a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or an organic tellurium compound represented by the general formula (3) and A block polymerization step of polymerizing a first monomer composition containing a (meth)acrylic vinyl monomer using a second mixture of an azo polymerization initiator and an organic ditelluride compound represented by general formula (4); and a B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by the general formula (1) using the first mixture or the second mixture, In all polymerization steps, the difference (T _1/2 -Tr) between the 10-hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) is 10°C to 60°C. characterized by

〔一般式（３）中、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表す。Ｒ³²およびＲ³³は、それぞれ、水素原子または炭素数１～８のアルキル基を表す。Ｒ³⁴は、炭素数１～８のアルキル基、アリール基、芳香族へテロ環基、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表す。
一般式（４）中、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表す。〕

[In 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 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, 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 general formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

In the method for producing a polymerization product of the present invention, in the presence of a first mixture of an organic tellurium compound and an azo polymerization initiator or a second mixture of an organic tellurium compound, an azo polymerization initiator and an organic ditelluride compound, , under mild conditions, block copolymers with precise molecular weights and molecular weight distributions can be synthesized by polymerizing the monomer composition. In addition, in the method for producing a block copolymer of the present invention, in all block polymerization steps, the difference between the 10-hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) ( T _1/2 -Tr) is adjusted to 10°C to 60°C. By adjusting the reaction temperature within the above range, purification of polymer impurities can be suppressed. Therefore, by adopting the method for producing a polymerized product of the present invention, a polymerized product having a desired high block copolymer content and a low polymer impurity content can be obtained.

The polymerized product of the present invention has excellent dispersing performance and excellent storage stability when used as a dispersant. The method for producing a polymerized product of the present invention provides a polymerized product having a desired high block copolymer content and a low polymer impurity content.

The polymerization product of the present invention is a polymerization product obtained by polymerizing a monomer composition, comprising an A block having a structural unit derived from a (meth)acrylic vinyl monomer, and general formula (1 ) contains a block copolymer having a B block having a structural unit represented by, the molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and the content of the block copolymer is 75% by mass or more in 100% by mass of the polymerized product.

The polymerization product of the present invention contains a block copolymer having an A block having a structural unit derived from a (meth)acrylic vinyl monomer and a B block having a structural unit represented by general formula (1). do. This block copolymer has an A block and a B block, and thus has excellent dispersibility. Thus, the polymerized product of the invention can be used as a dispersant. Moreover, the content of the block copolymer in the polymerization product of the present invention is 75% by mass or more. In other words, the content of polymer impurities, such as a polymer consisting only of A blocks and a polymer consisting only of B blocks, is 25 mass % or less. Therefore, the polymerized product of the present invention exhibits excellent storage stability when used as a dispersant.

An example of a preferred embodiment of the present invention will be described below. However, the following embodiments are merely examples. The present invention is by no means limited to the following embodiments.

<Polymerization product>
The polymerization product of the present invention contains block copolymers having A blocks and B blocks, and polymeric impurities.

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

In the present invention, the term "polymerization product" refers to a product obtained when polymerization (and optionally quaternization treatment) is performed to obtain the block copolymer. The "polymerization product" includes the desired block copolymer and polymer impurities by-produced when synthesizing the block copolymer.

In the present invention, "polymer impurities" are other polymers that are inevitably by-produced when synthesizing the desired block copolymer. For example, polymer impurities by-produced when synthesizing an AB diblock copolymer include random polymers having the same composition as the A block and random polymers having the same composition as the B block. Polymer impurities that are by-produced when synthesizing the ABA triblock copolymer or the BAB triblock copolymer include random polymers having the same composition as the A block, and the same as the B block. A random polymer having a composition of The "polymer impurity" is a polymer by-produced when synthesizing the desired block copolymer, and does not include a separately added polymer.

(Block copolymer)
Various constituent components of the block copolymer will be described below.

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

The content of structural units derived from the (meth)acrylic vinyl monomer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, based on 100% by mass of the A block. Particularly preferably, it is 100% by mass.

The (meth)acrylic vinyl monomers include (meth)acrylates having a chain alkyl group (straight-chain alkyl group or branched-chain alkyl group), (meth)acrylates having a cyclic alkyl group, and (meth)acrylates having a polycyclic structure. ) acrylate, (meth) 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, having an alkoxy group ( meth)acrylates, (meth)acrylates having an oxygen-containing heterocyclic group, (meth)acrylates having an acidic group, (meth)acrylic acid, and the like, and among these, one or two or more may be used in combination. can be used.

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

The (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group having 1 to 20 carbon atoms in the branched-chain alkyl group, and the branched-chain alkyl group having 1 to 20 carbon atoms. (Meth)acrylates with branched alkyl groups of 10 are preferred. Examples of (meth)acrylates having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate and the like.

The (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Cyclic alkyl groups include cyclic alkyl groups having a monocyclic structure (eg, cycloalkyl groups). Specific examples of (meth)acrylates having a cyclic alkyl group with 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 with 6 to 12 carbon atoms. Polycyclic structures include cyclic alkyl groups having a bridged ring structure (eg, adamantyl, norbornyl, and isobornyl groups). Specific examples of (meth)acrylates having a polycyclic structure include isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-methyl-2-adamantyl (Meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate and the like.

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

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

The (meth)acrylates having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- Hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate and the like.

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

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

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

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 ), a phosphinic acid group (-- PO ₂ H ₂ ). As the (meth)acrylate having an acidic group, a (meth)acrylate having a carboxy group such as a monomer obtained by reacting a hydroxyalkyl (meth)acrylate with an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride. ; (meth) acrylate having a sulfonic acid group such as ethyl sulfonate (meth) acrylate; (meth) acrylate having a phosphoric acid group such as 2-(phosphonooxy) ethyl (meth) acrylate; is a (meth)acrylate having a carboxy group.

The (meth)acrylic vinyl monomer preferably contains a (meth)acrylate having a polyalkylene glycol structural unit and/or a (meth)acrylate having a lactone-modified hydroxy group. When using these monomers, the total content of structural units derived from (meth)acrylates having a polyalkylene glycol structural unit in the A block and (meth)acrylates having a lactone-modified hydroxy group is In 100% by mass of the A block, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less. , more preferably 70% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

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

As one aspect of the (meth)acrylic vinyl monomer, the (meth)acrylic vinyl monomer has a (meth)acrylate having a chain alkyl group (straight-chain alkyl group or branched-chain alkyl group) or a cyclic alkyl group. (meth)acrylate having a polycyclic structure, (meth)acrylate having an aromatic group, (meth)acrylate having a hydroxy group, (meth)acrylate having an alkoxy group, oxygen-containing heterocyclic group (meth) acrylate having an acidic group, (meth) acrylate having an acidic group, one or more selected from (meth) acrylic acid, and (meth) acrylate having a polyalkylene glycol structural unit. . Dispersibility and dispersion stability can be further improved by using these (meth)acrylic vinyl monomers. In this case, the content of the structural unit derived from (meth)acrylate having a polyalkylene glycol structural unit is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 100% by mass of the A block. is 20% by mass or more, preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

As another aspect of the (meth)acrylic vinyl monomer, the (meth)acrylic vinyl monomer is a (meth)acrylate having a chain alkyl group (straight-chain alkyl group or branched-chain alkyl group), a cyclic alkyl group (meth) acrylates having a polycyclic structure, (meth) acrylates having an aromatic group, (meth) acrylates having a hydroxy group, (meth) acrylates having an alkoxy group, oxygen-containing heterocycles (meth) acrylate having a group, (meth) acrylate having an acidic group, one or more selected from (meth) acrylic acid, and (meth) acrylate having a lactone-modified hydroxy group. . Dispersibility, heat resistance and alkali developability can be improved by using these (meth)acrylic vinyl monomers. In this case, the total content of structural units derived from a (meth)acrylate having a lactone-modified hydroxyalkyl group in the A block is preferably 5% by mass or more, more preferably 30% by mass, based on 100% by mass of the A block. % or more, preferably 80% by mass or less, more preferably 70% by mass or less.

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

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

[In the general formula (7), n7 represents an integer of 2 to 150. R ⁷¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁷² represents an alkylene group having 1 to 6 carbon atoms. ^R73 represents a hydrogen atom or a methyl group. ]

n7 in the formula (7) is preferably an integer of 2-50, more preferably an integer of 2-10.
The alkyl group having 1 to 6 carbon atoms represented by R ⁷¹ may be linear or branched, preferably linear. Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁷¹ include methyl group, ethyl group, n-propyl group, n-butyl group, pentyl group and hexyl group. R ⁷¹ is preferably an alkyl group having 1 to 3 carbon atoms.
The alkylene group having 1 to 6 carbon atoms represented by R ⁷² may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 6 carbon atoms represented by R ⁷² include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group. R ⁷² is preferably an alkylene group having 2 to 4 carbon atoms.

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

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

[In the general formula (8), n8 represents an integer of 1 to 10. R ⁸¹ represents an alkylene group having 1 to 10 carbon atoms. R ⁸² represents an alkylene group having 1 to 10 carbon atoms. ^R83 represents a hydrogen atom or a methyl group. ]

n8 in the formula (8) is preferably an integer of 1-7, more preferably an integer of 1-5.
The alkylene group having 1 to 10 carbon atoms represented by R ⁸¹ may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁸¹ include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, A nonamethylene group, a decamethylene group, and the like can be mentioned. R ⁸¹ is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 3 to 8 carbon atoms.
The alkylene group having 1 to 10 carbon atoms represented by R ⁸² may be linear or branched, but is preferably linear. Specific examples of the alkylene group having 1 to 10 carbon atoms represented by R ⁸² include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, 1-methylethylene group and the like. R ⁸² is preferably an alkylene group having 1 to 5 carbon atoms.

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

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

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

The A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably (meth)acrylate or (meth)acrylic acid having an acidic group. By having a structural unit derived from a vinyl monomer having an acidic group, the solubility in an alkaline developer is increased, and the alkaline developability can be improved. However, when the proportion is increased, there is a possibility that the affinity with the solvent and the alkali-soluble resin will be lowered. Therefore, the ratio of the structural units derived from the vinyl monomer having an acidic group is preferably such that the overall acid value of the block copolymer is lower than the amine value.

When a structural unit derived from a vinyl monomer having an acidic group is contained, the content thereof is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more in 100% by mass of the A block. , preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less. If the content of the structural unit derived from a vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate becomes faster when neutralized with alkali in alkaline development, and if it is 20% by mass or less, hydrophilicity is high. Therefore, it is possible to prevent the formed pixels from becoming disorderly.

The A block contains less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less of a structural unit represented by the general formula (1) described later, and in the general formula (1) It is more preferable not to contain the represented structural unit. The lower the content of the structural unit represented by formula (1) in the A block, the better the dispersibility of the coloring material.

The A block preferably has no amino group. In other words, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group. When a large amount of amino groups are present in the A block, the colorant is adsorbed to both the A block and the B block when used as a dispersant, resulting in a decrease in the dispersibility of the colorant. The content of structural units derived from a vinyl monomer having an amino group in the A block (including those in which the amino group is quaternized) is preferably 2% by mass or less, more preferably 1% by mass or less, More preferably 0.1% by mass or less, most preferably 0% by mass.

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

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

(Structural unit represented by general formula (1))
The structural unit represented by general formula (1) may be of one kind or may be of two or more kinds. By using the structural unit represented by the general formula (1), the adsorbability to the coloring material is high, and the heat resistance can be increased.

〔式（１）において、Ｒ¹¹およびＲ¹²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹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。Ｘ¹は２価の連結基を示す。Ｒ¹³は水素原子またはメチル基を示す。〕

[In formula (1), R ¹¹ and R ¹² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may combine with each other to form a cyclic structure. X ¹ represents a divalent linking group. ^R13 represents a hydrogen atom or a methyl group. ]

The chain hydrocarbon group represented by R ¹¹ or R ¹² includes both linear and branched chains. Examples of substituents of the chain hydrocarbon group represented by R ¹¹ or R ¹² include a halogen group, an alkoxy group, a benzoyl group (--COC ₆ H ₅ ), and a hydroxy group. Examples of substituents of the cyclic hydrocarbon group represented by R ¹¹ or R ¹² include chain alkyl groups, halogen groups, alkoxy groups, and hydroxy groups.

The group represented by R ¹¹ or R ¹² includes an optionally substituted alkyl group having 1 to 4 carbon atoms and an optionally substituted aralkyl group having 7 to 16 carbon atoms. Preferred are methyl group, ethyl group, propyl group and benzyl group (--CH ₂ C ₆ H ₅ ).

Examples of the cyclic structure formed by combining R ¹¹ or R ¹² include a 5- to 7-membered nitrogen-containing hetero ring or a condensed ring formed by condensing two of these. The nitrogen-containing heterocyclic ring preferably has no aromaticity, more preferably a saturated ring. Specific examples include structures represented by the following formulas (1-1), (1-2), and (1-3).

〔一般式（１－１）、（１－２）、（１－３）において、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 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 of 0 to 5; m represents an integer of 0 to 4; n represents an integer of 0 to 4; * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ¹⁴ may be the same or different. ]

In the general formula (1), the divalent linking group X ¹ includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a --CONH--R ¹⁵ -- group (amide group), --COO--R ¹⁶ -- groups (ester groups) and the like, preferably -COO-R ¹⁶ - and/or -CONH-R ¹⁵ -, more preferably -COO-R ¹⁶ -. ^The bonding direction of ^the amide group and the ester group is not particularly ^limited . --OR ¹⁶ --NR ¹¹ R ¹² is preferred.
R ¹⁵ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.
R ¹⁶ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

Specific examples of the vinyl monomer forming the structural unit represented by formula (1) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, ) acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide and the like.

The content of the structural unit represented by the general formula (1) is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more in 100% by mass of the B block, and is 98% by mass. % or less, more preferably 70 mass % or less, still more preferably 65 mass % or less, and particularly preferably 60 mass % or less. By setting the content of the structural unit represented by the general formula (1) within this range, it is considered to have a high affinity with the coloring material.

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

〔式（２）において、Ｒ²¹、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示す。Ｒ²¹、Ｒ²²およびＲ²³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In Formula (2), R ²¹ , R ²² and R ²³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ²¹ , R ²² and R ²³ may combine with each other to form a cyclic structure. X ² represents a divalent linking group. ^R24 represents a hydrogen atom or a methyl group. Y ⁻ represents a counterion. ]

The chain hydrocarbon groups represented by R ²¹ to R ²³ include both linear and branched chains. A halogen group, an alkoxy group, a benzoyl group, a hydroxy group and the like can be mentioned as the substituents possessed by the chain hydrocarbon groups represented by R ²¹ to R ²³ . Examples of substituents possessed by the cyclic hydrocarbon groups represented by R ²¹ to R ²³ include chain alkyl groups, halogen atoms, alkoxy groups, and hydroxy groups.

Examples of the groups represented by R ²¹ to R ²³ include an optionally substituted alkyl group having 1 to 4 carbon atoms and an optionally substituted aralkyl group having 7 to 16 carbon atoms. Preferred are methyl group, ethyl group, propyl group and benzyl group.

Examples of the cyclic structure formed by bonding two or more of R ²¹ to R ²³ together include a 5- to 7-membered nitrogen-containing hetero ring or a condensed ring formed by condensing two of these. be done. The nitrogen-containing heterocyclic ring preferably has no aromaticity, more preferably a saturated ring. Specific examples include structures represented by the following formulas (2-1), (2-2), and (2-3).

〔一般式（２－１）、（２－２）、（２－３）において、Ｒ²⁵は、Ｒ²¹～Ｒ²³のいずれかである。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 general formulas (2-1), (2-2) and (2-3), R ²⁵ is any one of R ²¹ to R ²³ . R ²⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4; n represents an integer of 0 to 4; * represents a bond. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ²⁶ may be the same or different. ]

In the general formula (2), the divalent linking group X ² includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ²⁷ — group (amide group), and a —COO—R ²⁸ — group. (ester group) and the like, preferably -CONH-R ²⁷ - and/or -COO-R ²⁸ -, more preferably -COO-R ²⁸ -. Although the bonding direction of the amide group and the ester group is not particularly limited, the bonding mode of the amide group is preferably C—CO—NH—R ²⁷ —N ⁺ R ²¹ R ²² R ²³ , and the bonding mode of the ester group is , C—CO—O—R ²⁸ —N ⁺ R ²¹ R ²² R ²³ are preferred.
R ²⁷ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.
R ²⁸ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, more preferably is an alkylene group having 1 to 4 carbon atoms. Specific examples include a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group and the like.

Y ⁻ includes halogen anions, carboxylate anions, nitroxide anions, sulfate anions, sulfonate anions, phosphate anions, alkylphosphate anions, and the like.
Examples of the halogen anions include fluoroanions, chloroanions, bromoanions, and iodine anions.
Examples of the alkyl carboxylate anions include alkyl carboxylate anions such as acetate anions and propionate anions; aromatic carboxylate anions such as benzoate anions.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; and aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkylsulfonate anions such as methanesulfonate anion and ethanesulfonate anion; and aromatic sulfonate anions such as benzenesulfonate anion and toluenesulfonate anion.

Specific examples of the vinyl monomer forming the structural unit represented by formula (2) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxypropyltrimethylammonium chloride, and (meth)acryloyloxybutyltrimethylammonium chloride. , (meth)acryloyloxyethylbenzyldimethylammonium chloride, (meth)acryloyloxypropylbenzyldimethylammonium chloride, (meth)acryloyloxybutylbenzyldimethylammonium chloride, (meth)acryloyloxyethylbenzyldiethylammonium chloride, (meth)acryloyloxy Propylbenzyldiethylammonium chloride, (meth)acryloyloxybutylbenzyldiethylammonium chloride, (meth)acryloylamidopropylbenzyldimethylammonium chloride, (meth)acryloyloxyethyltrimethylammonium bromide, (meth)acryloyloxypropyltrimethylammonium bromide, (meth) ) Acryloyloxybutyltrimethylammonium bromide, (meth)acryloyloxyethylbenzyldimethylammonium bromide, (meth)acryloyloxypropylbenzyldimethylammonium bromide, (meth)acryloyloxybutylbenzyldimethylammonium bromide, (meth)acryloyloxyethylbenzyldimethylammonium bromide Bromide, (meth)acryloyloxypropylbenzyldiethylammonium bromide, (meth)acryloyloxybutylbenzyldiethylammonium bromide, (meth)acryloylamidopropylbenzyldimethylammonium bromide, (meth)acryloyloxyethyltrimethylammonium iodide, (meth)acryloyl Oxypropyltrimethylammonium iodide, (meth)acryloyloxybutyltrimethylammonium iodide, (meth)acryloyloxyethylbenzyldimethylammonium iodide, (meth)acryloyloxypropylbenzyldimethylammonium iodide, (meth)acryloyloxybutylbenzyldimethylammonium iodide ammonium iodide, (meth)acryloyloxyethylbenzyldiethylammonium iodide, (meth)acryloyloxypropylbenzyldiethylammonium iodide, (Meth)acryloyloxybutylbenzyldiethylammonium iodide, (meth)acryloyloxyethyltrimethylammonium fluoride, (meth)acryloyloxypropyltrimethylammonium fluoride, (meth)acryloyloxybutyltrimethylammonium fluoride, (meth)acryloyloxy Ethylbenzyldimethylammonium fluoride, (meth)acryloyloxypropylbenzyldimethylammonium fluoride, (meth)acryloyloxybutylbenzyldimethylammonium fluoride, (meth)acryloyloxyethylbenzyldiethylammonium fluoride, (meth)acryloyloxypropylbenzyl Diethylammonium fluoride, (meth)acryloyloxybutylbenzyldiethylammonium fluoride, (meth)acryloyloxyethyltrimethylammonium methyl sulfate, (meth)acryloyloxypropyltrimethylammonium methylsulfate, (meth)acryloyloxybutyltrimethyl ammonium = methylsulfate, (meth) acryloyloxyethyldimethylethylammonium = ethylsulfate, (meth)acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth)acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth) ) acryloyloxyethyltrimethylammonium = toluene-4-sulfonate, (meth) acryloyloxypropyltrimethylammonium = toluene-4-sulfonate, (meth) acryloyloxybutyltrimethylammonium = toluene-4-sulfonate, (meth) acryloylamidopropyltrimethyl ammonium=methylsulfate, (meth)acryloylamidopropylethyldimethylammonium=ethylsulfate and the like.

When the structural unit represented by the general formula (2) is contained, the content thereof is preferably 15% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more in 100% by mass of the B block. , preferably 99% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. By setting the content of the structural unit represented by the general formula (2) within this range, it is believed to have a high affinity with the coloring material.

The B block may contain only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may contain other structural units. From the viewpoint of maintaining affinity with the coloring material, the total content of the structural unit represented by general formula (1) and the structural unit represented by general formula (2) in block B is 80% by mass or more. is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more. Moreover, it is preferable that the B block does not substantially contain a structural unit derived from a vinyl monomer having an acidic group. That is, the content of structural units derived from a vinyl monomer having an acidic group is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less in 100% by mass of B block.

Specific examples of the vinyl monomer that can form other structural units of the B block are the same as the specific examples of the vinyl monomer that can form other structural units of the A block.

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

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement), 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 group consisting of (AB) _m type, (AB) _m -A type, (B-A) _m -B type (m is an integer of 1 or more, for example an integer of 1 to 3) A copolymer having at least one structure selected from is preferred. Among these, AB type diblock copolymers are preferred from the viewpoint of handling during processing and physical properties of the composition. By constituting an AB type diblock copolymer, a structural unit derived from a (meth)acrylic vinyl monomer in the A block and a structural unit represented by the general formula (1) in the B block are combined. It is believed that it can be localized and efficiently act favorably with the colorant, the 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 the A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 85% by mass or less, based on 100% by mass of the entire block copolymer. More preferably 80% by mass or less, still more preferably 75% by mass or less. The content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 65% by mass or less, based on 100% by mass of the entire block copolymer. More preferably 60% by mass or less, still more preferably 55% by mass or less. By adjusting the content of the A block and the B block within the above range, the dispersing performance is further improved when used as a dispersant.

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

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, more preferably 2% by mass or more, still more preferably 3% by mass or more, and 10% by mass. The following is preferable, more preferably 9% by mass or less, and still more preferably 8% by mass or less.

The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer is preferably 5% by mass or more, more preferably 10% by mass. Above, 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 content of the block copolymer in the polymerization product is 75% by mass or more, preferably 80% by mass or more, more preferably 82% by mass or more, based on 100% by mass of the polymerization product. If the content of the block copolymer in the polymerization product is 75% by mass or more, storage stability is improved when the polymerization product is used as a dispersant.

When the polymerization product is obtained for the purpose of synthesizing an AB diblock copolymer, the content of the AB diblock copolymer in the polymerization product is In 100% by mass, it is 75% by mass or more, preferably 80% by mass or more, and more preferably 82% by mass or more.

When the polymerization product is obtained for the purpose of synthesizing an ABA triblock copolymer or a BAB triblock copolymer, AB in the polymerization product -The total content of the A triblock copolymer and the AB diblock copolymer is 75% by mass or more, preferably 80% by mass or more, more preferably 82% by mass or more in 100% by mass of the polymerization product be.

The weight average molecular weight (Mw) of the polymerization product is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and preferably 40,000 or less, more preferably 30,000. 20,000 or less, more preferably 20,000 or less. If the weight-average molecular weight is within the above range, the dispersion performance when used as a dispersant will be better. The molecular weight of the polymerization product is measured by a gel permeation chromatography (hereinafter referred to as "GPC") method.

The molecular weight distribution (PDI) of the polymerization product is 2.0 or less, more preferably 1.6 or less, and even more preferably 1.4 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of polymerization product)/(number average molecular weight (Mn) of polymerization product). The smaller the PDI, the narrower the width of the molecular weight distribution and the more uniform the molecular weight of the polymerization product. If the molecular weight distribution (PDI) of the polymerized product exceeds 2.0, it will contain those with small molecular weights and those with large molecular weights.

The amine value of the polymerization product is preferably 3 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 20 mgKOH/g or more, particularly preferably 30 mgKOH/g or more, and more preferably 180 mgKOH/g or less. It is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less. By setting the amine value within the above range, the dispersing performance is further improved when used as a dispersant.

The acid value of the polymerized product is preferably less than 35 mgKOH/g. If the acid value exceeds the above range, there is a risk that the dispersibility will deteriorate due to interaction between the block copolymers.

<Method for producing polymerized product>
The polymerization product of the present invention is produced by sequentially polymerizing the vinyl monomers that constitute the blocks, thereby first producing the A block, and then polymerizing the B block monomers onto the A block; A method of polymerizing a block A monomer onto a block B; A method of quaternizing a portion of the tertiary amine structure of the structural unit represented by formula (1) in the resulting polymer; a vinyl monomer capable of forming the structural unit represented by formula (1) in the B block A monomer composition containing is polymerized, the A block monomer is polymerized in this polymer, and a part of the tertiary amine structure of the structural unit represented by formula (1) in the obtained polymer is converted to a quaternary and the like.

Examples of methods for producing a polymerization product by a polymerization reaction of a vinyl monomer include living polymerization methods such as a living anion polymerization method, a living cationic polymerization method, and a living radical polymerization method. It is preferred to manufacture things. Living anionic polymerization and living cationic polymerization require strict polymerization conditions, and the functional groups that can co-exist are limited. It is preferable because the molecular weight distribution can be precisely controlled and a polymer with a uniform composition can be produced while maintaining the simplicity that is not affected by the That is, the block copolymer is preferably polymerized by living radical polymerization.

In addition, in the conventional radical polymerization method, not only initiation reaction and propagation reaction but also termination reaction and chain transfer reaction cause deactivation of the propagating end, and tend to result in a mixture of polymers with various molecular weights and non-uniform compositions. . On the other hand, the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method. It is preferable in that it is easy to precisely control and manufacture a polymer with a uniform composition.

Living radical polymerization methods include a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); method (TERP method); Since the ATRP method uses an amine-based complex, it may not be possible to use it without protecting the acidic group of the vinyl monomer having an acidic group. In the RAFT method, when a variety of monomers are used, it is difficult to obtain a low molecular weight distribution, and problems such as sulfur odor and coloration may occur. Among these methods, it is preferable to use the TERP method from the viewpoint of the diversity of usable monomers, molecular weight control in the high molecular region, uniform composition, or 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. 2004/072126 and methods described in WO 2004/096870.

Specific polymerization methods for the TERP method include the following (a) to (d).
(a) A vinyl monomer is polymerized using an organic tellurium compound represented by general formula (3).
(b) polymerizing a vinyl monomer using a first mixture of an organic tellurium compound represented by general formula (3) and an azo polymerization initiator;
(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (3) and an organic ditelluride compound represented by general formula (4).
(d) polymerizing a vinyl monomer using a second mixture of an organic tellurium compound represented by general formula (3), an azo polymerization initiator, and an organic ditelluride compound represented by general formula (4);

〔一般式（３）中、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表す。Ｒ³²およびＲ³³は、それぞれ、水素原子または炭素数１～８のアルキル基を表す。Ｒ³⁴は、炭素数１～８のアルキル基、アリール基、芳香族へテロ環基、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表す。
一般式（４）中、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表す。〕

[In 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 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, 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 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 specific examples are as follows.
Examples of 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. linear or branched alkyl groups such as radicals, octyl groups, and cyclic alkyl groups such as cyclohexyl groups. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
A phenyl group, a naphthyl group, etc. can be mentioned as an aryl group.
A pyridyl group, a furyl group, a thienyl group, etc. can be mentioned as an aromatic heterocyclic group.

The groups represented by R ³² and R ³³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and specific examples of each group are as follows.
Examples of 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. linear or branched alkyl groups such as radicals, octyl groups, and cyclic alkyl groups such as cyclohexyl groups. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

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 It is a propargyl group, specifically as follows.
Examples of 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. linear or branched alkyl groups such as octyl groups, cyclic alkyl groups such as cyclohexyl groups, and the like. A linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
A phenyl group, a naphthyl group, etc. can be mentioned as an aryl group. A phenyl group is preferred.
Examples of the substituted aryl group include a phenyl group having a substituent, a naphthyl group having a substituent, and the like. Examples of the substituents of the aryl group having the above substituents include halogen atoms, hydroxy groups, alkoxy groups, amino groups, nitro groups, cyano groups, and carbonyl-containing groups represented by —COR ³¹¹ (R ³¹¹ is a carbon 1-8 alkyl groups, aryl groups, C1-8 alkoxy groups or aryloxy groups), sulfonyl groups, trifluoromethyl groups and the like. Moreover, it is preferable that one or two of these substituents are substituted.
A pyridyl group, a furyl group, a thienyl group, etc. can be mentioned as an aromatic heterocyclic group.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom. butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
Acyl groups include acetyl, propionyl, and benzoyl groups.
Examples of amide groups include -CONR ³²¹ R ³²² (R ³²¹ and R ³²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
The oxycarbonyl group is preferably a group represented by —COOR ³³¹ (R ³³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group), such as a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl groups.
The allyl group includes -CR ³⁴¹ R ³⁴² -CR ³⁴³ =CR ³⁴⁴ R ³⁴⁵ (R ³⁴¹ and R ³⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R ³⁴³ , R ³⁴⁴ and R ³⁴⁵ are , each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and each substituent may be connected in a cyclic structure).
The propargyl group includes —CR ³⁵¹ R ³⁵² —C≡CR ³⁵³ (R ³⁵¹ and R ³⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁵³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms , an aryl group or a silyl group) and the like.

Specifically, the organic tellurium compound represented by the general formula (3) is (methyltheranylmethyl)benzene, (methyltheranylmethyl)naphthalene, ethyl-2-methyl-2-methyltheranyl-propionate, ethyl-2- methyl-2-n-butyltheranyl-propionate, (2-trimethylsiloxyethyl)-2-methyl-2-methyltheranyl-propionate, (2-hydroxyethyl)-2-methyl-2-methyltheranyl-propionate or (3-trimethylsilylpropargyl )-2-methyl-2-methylteranyl-propionate, etc., organic All tellurium compounds can be exemplified.

Specific examples of the organic ditelluride compound represented by the general formula (4) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, di -n-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis-(p-methoxyphenyl) ditelluride, bis-(p-aminophenyl) ditelluride, bis -(p-nitrophenyl)ditelluride, bis-(p-cyanophenyl)ditelluride, bis-(p-sulfonylphenyl)ditelluride, dinaphthylditelluride, dipyridylditelluride and the like can be exemplified.

As the azo polymerization initiator, any azo polymerization initiator that is commonly used in radical polymerization can be used without any particular limitation. For example, 2,2′-azobis(isobutyronitrile) (AIBN) (65° C., toluene), 2,2′-azobis(2-methylbutyronitrile) (AMBN) (67° C., toluene), 2, 2′-azobis(2,4-dimethylvaleronitrile) (ADVN) (52° C., toluene), 1,1′-azobis(1-cyclohexanecarbonitrile) (ACHN) (88° C., toluene), dimethyl-2, 2′-azobis isobutyrate (MAIB) (66° C., toluene), 4,4′-azobis(4-cyanovaleric acid) (ACVA) (69° C., water (as Na salt)), 1,1′ -azobis(1-acetoxy-1-phenylethane) (61°C, toluene), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70) (30°C, toluene), 2,2′-azobis(2-methylamidinopropane) dihydrochloride (56° C., water), 2,2′-azobis[2-(2-imidazolin-2-yl)propane] (61° C., methanol), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (86° C., water),
2,2′-azobis(N-butyl-2-methylpropionamide) (110° C., ethylbenzene), or dimethyl 1,1′-azobis(1-cyclohexanecarboxylate) (73° C., toluene), etc. can be done. Among these, the azo polymerization initiator is preferably an oil-soluble azo polymerization initiator, more preferably AIBN, AMBN, ADVN, ACHN, or V-70. The numbers in parentheses after the compound names of the above azo polymerization initiators are the 10-hour half-life temperature and the solvent used for the measurement of the 10-hour half-life temperature. The 10-hour half-life temperature of the azo polymerization initiator refers to the temperature at which the concentration of the azo group in the solvent is halved in 10 hours. Solvents used for measuring the half-life temperature include toluene, ethylbenzene, etc. for oil-soluble azo polymerization initiators, and water, methanol, etc. for water-soluble azo polymerization initiators.

In the polymerization step, in a vessel purged with an inert gas, the vinyl monomer and the organotellurium compound of general formula (3) are added to the vinyl monomer for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution, etc., according to the type of the vinyl monomer. An azo polymerization initiator and/or an organic ditelluride compound of general formula (4) are mixed. At this time, examples of the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferred.

The amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the intended copolymer. It is preferable to use 5 mol to 10000 mol of the vinyl monomer per 1 mol of the organic tellurium compound of general formula (3).

When the organotellurium compound represented by the general formula (3) of (b) and an azo polymerization initiator are used in combination, the amount of the azo compound is 0.01 mol to 10 mol per 1 mol of the organotellurium compound represented by the general formula (3). is preferred.

When the organic tellurium compound of general formula (3) in (c) and the organic ditelluride compound of general formula (4) are used in combination, the organic tellurium compound of general formula (4) is used per 1 mol of the organic tellurium compound of general formula (3). The amount of the ditelluride compound is preferably 0.01 mol to 100 mol.

When the organic tellurium compound of general formula (3) in (d) above, the organic ditelluride compound of general formula (4), and an azo polymerization initiator are used in combination, generally per 1 mol of the organic tellurium compound of general formula (3) The organic ditelluride compound of formula (4) is preferably 0.01 mol to 100 mol, and the azo polymerization initiator is preferably 0.01 mol to 10 mol per 1 mol of the organic tellurium compound of general formula (3).

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

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

The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting copolymer, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours. The TERP method can obtain high yields and precise molecular weight distributions even at low polymerization temperatures and short polymerization times. At this time, the pressure is usually normal pressure, but may be pressurized or reduced.

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

The growing terminal of the copolymer obtained by the polymerization reaction is in the form of —TeR ³¹ (wherein R ³¹ is the same as R ³¹ in general formula (3)) derived from the tellurium compound, and the polymerization reaction is terminated. Although it is deactivated by later operation in air, tellurium atoms may remain. Since a copolymer having a tellurium atom remaining at the end thereof is colored or has poor thermal stability, it is preferable to remove the tellurium atom.

Methods for removing tellurium atoms include radical reduction methods using tributylstannane or thiol compounds; adsorption methods using activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbents, etc.; ion exchange resins, etc. Method of adsorbing metals: Hydrogen peroxide solution or peroxides such as benzoyl peroxide are added, air or oxygen is blown into the system to oxidize and decompose the tellurium atoms at the ends of the copolymer, washing with water or appropriate A liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration that extracts and removes only those with a specific molecular weight or less; , or a combination of these methods can be used.

When the tertiary amine group of the structural unit represented by formula (1) is quaternized, quaternizing agents include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; benzyl chloride; , benzyl bromide, benzyl iodide and other aralkyl halides; diaryl sulfates such as diphenyl sulfate; dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate; methyl p-toluenesulfonate, p-toluenesulfonic acid aromatic alkyl sulfonates such as ethyl; and the like. Among these, aralkyl halides such as benzyl chloride, benzyl bromide, and benzyl iodide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate, methyl p-toluenesulfonate, and p-toluenesulfone are preferred. Aromatic alkyl sulfonates such as ethyl acetate, more preferably benzyl chloride, dimethyl sulfate and methyl p-toluenesulfonate. Alkyl groups and aralkyl groups 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, aralkyl group, etc. introduced by the quaternization.

As a method for quaternizing a part of the tertiary amine structure of the structural unit represented by formula (1) in the polymer, there is 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 formula (1), adding a quaternizing agent to the reaction solution, and stirring the reaction solution may be mentioned. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 25° C. to 65° C., and the stirring time is preferably 1 hour to 40 hours. It is also preferable to dilute the reaction solution after polymerization when adding the quaternizing agent. Examples of the solvent added for dilution include a solvent that can be used in the polymerization reaction, a protic solvent, and a mixed solvent of a solvent that can be used in the polymerization reaction and a protic solvent. can be selected as appropriate. Methanol is preferred as the protic solvent.

(Preferred embodiment of method for producing polymerization product)
One aspect of the method for producing the polymerized product will be described below.

The production method includes a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator. A block polymerization step of polymerizing a first monomer composition containing a (meth)acrylic vinyl monomer using a second mixture with an organic ditelluride compound represented by the general formula (4), and the first mixture or A B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by general formula (1) using the second mixture, and in all the polymerization steps, The difference (T _1/2 -Tr) between the 10-hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) is preferably 10° C. to 60° C., more preferably 10°C to 50°C, more preferably 10°C to 40°C, particularly preferably 10°C to 30°C.

Generally, in the TERP method, if a monomer has an amino group or an acidic group, these amino groups or acidic groups tend to deactivate the polymerization terminal radicals. For example, an amino group can provide a hydrogen radical to deactivate a polymerized terminal radical. In addition, with an acidic group, proton coordination to the organic tellurium that forms dormant species occurs, which may inhibit the formation of dormant species and deactivate the polymer terminal. Therefore, when the monomer has an amino group or an acidic group, the content of the polymer to which each block component is not bonded (“unconnected component”) tends to increase in the polymerization product. However, by setting the polymerization temperature to a temperature that is 10° C. or more lower than the 10-hour half-life temperature of the azo polymerization initiator to be added, it is possible to suppress the formation of unconnected components.

In said preferred embodiment, either the first mixture or the second mixture is used during the polymerization. These first mixture and second mixture are used in common in the A block polymerization step and the B block polymerization step. That is, for example, when producing an AB diblock copolymer, after performing the first-stage polymerization step, this reaction solution (the first-stage polymer, the first mixture or the second mixture containing.) is added to the monomer composition of the second stage, and the second stage polymerization step is performed.

In the first mixture, the amount of the azo polymerization initiator used is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.05 mol or more, relative to 1 mol of the organic tellurium compound of general formula (3). It is 1 mol or more, preferably 10 mol or less, more preferably 2 mol or less, further preferably 1 mol or less.

In the second mixture, the amount of the azo polymerization initiator used is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.05 mol or more, relative to 1 mol of the organic tellurium compound of general formula (3). It is 1 mol or more, preferably 10 mol or less, more preferably 2 mol or less, further preferably 1 mol or less.

In the second mixture, the amount of the organic ditelluride compound of general formula (4) used is preferably 0.01 mol or more, more preferably 0.1 mol or more, and further preferably 0.1 mol or more per 1 mol of the organic tellurium compound of general formula (3). It is preferably 0.2 mol or more, preferably 100 mol or less, more preferably 5 mol or less, and still more preferably 3 mol or less.

In the A block polymerization step, a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator A second mixture of the agent and the organic ditelluride compound represented by general formula (4) is used to polymerize a first monomer composition containing a (meth)acrylic vinyl monomer.

In the A block polymerization step, the amount of the vinyl monomer used is preferably 5 mol or more, more preferably 10 mol or more, still more preferably 20 mol or more, and preferably 10000 mol or less per 1 mol of the organic tellurium compound of general formula (3). , more preferably 300 mol or less, still more preferably 100 mol or less.

In the B block polymerization step, a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator Polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by general formula (1) using a second mixture of the agent and the organic ditelluride compound represented by general formula (4) .

In the B block polymerization step, the amount of the vinyl monomer used is preferably 5 mol or more, more preferably 7 mol or more, still more preferably 10 mol or more, and preferably 10000 mol or less per 1 mol of the organic tellurium compound of general formula (3). , more preferably 300 mol or less, still more preferably 100 mol or less.

In the preferred embodiment, the difference (T _1/2 -Tr) between the 10-hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) of all the polymerization steps is 10° C. or more. 60° C. or lower, preferably 50° C. or lower, more preferably 40° C. or lower, and particularly preferably 30° C. or lower. When a plurality of azo polymerization initiators are used, the 10-hour half-life temperature of all azo polymerization initiators preferably satisfies the above range.

In the preferred embodiment, the reaction temperature is preferably 0° C. or higher, more preferably 10° C. or higher, still more preferably 20° C. or higher, particularly preferably 30° C. or higher, and preferably 70° C. or lower, more preferably 60° C. or higher. °C or less, more preferably 55°C or less. The reaction time is preferably 1 hour or longer, more preferably 3 hours or longer, still more preferably 5 hours or longer, and preferably 100 hours or shorter, more preferably 50 hours or shorter, and still more preferably 30 hours or shorter.

In the preferred embodiment, the polymerization rate (monomer conversion rate) of the monomer in the monomer composition that is the raw material in each polymerization step is preferably 90% by mass or more, more preferably 96% by mass or more, and still more preferably 97% by mass. It is at least 98% by mass, particularly preferably at least 98% by mass.

The preferred embodiment has at least an A block polymerization step and a B block polymerization step. The order of these polymerization steps is not particularly limited, and the A block polymerization step may be performed first and then the B block polymerization step, or the B block polymerization step may be performed first and then the A block polymerization step. good too. Moreover, the preferred embodiment may have a step of polymerizing blocks other than the A block and the B block. Moreover, the preferred embodiment may have a step of quaternizing the structural unit represented by the general formula (1).

<Dispersant>
The dispersant of the present invention contains the polymerization product as a main component (50% by mass or more), preferably contains 75% by mass or more of the polymerization product, more preferably the polymerization product Consists only of things. The block copolymer contained in the polymerization product is, for example, a coloring material in which the tertiary amino group and quaternary ammonium base in the structure (B block) are treated with an acidic coloring material or an acidic group-containing dye derivative. It is believed that the B block strongly binds to the acidic group and adsorbs to the colorant, thereby exhibiting the effect of enhancing the dispersibility of the colorant. That is, the dispersant of the present invention is a component that disperses the colorant well by this action, so the type of colorant to be dispersed is not particularly limited. The dispersant of the present invention can be suitably used as a dispersant for color filters. The dispersant of the present invention can be more preferably used as a dispersant for color filters because it has alkali developability.

(Coloring composition)
The coloring composition of the present invention contains the dispersant, colorant, dispersion medium and binder resin.

(colorant)
The type of the coloring material may be appropriately selected according to its use, and examples thereof include pigments and dyes. From the viewpoint of light resistance and heat resistance, the coloring composition preferably contains a pigment as a coloring agent. As the pigment, either an organic pigment or an inorganic pigment may be used, but an organic pigment containing an organic compound as a main component is particularly preferable. Examples of pigments include pigments of various colors such as red pigments, yellow pigments, orange pigments, blue pigments, green pigments, and purple pigments. The structure of the pigment includes azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, and indigo pigments. polycyclic pigments such as polycyclic pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. The coloring material contained in the coloring composition may be of only one type, or may be of a plurality of types for adjustment of chromaticity and the like.

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, 168, 177, red pigments such as 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 C.I. I. Orange pigments such as C.I. Pigment Orange 36, 38, 43; I. Blue pigments such as C.I. Pigment Blue 15, 15:2, 15:3, 15:4, 15:6, 16, 22, 60; I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyloxyaluminum phthalocyanine, diphenylphosphinyloxyaluminum phthalocyanine, polyhalogenated diphenoxy Green pigments such as phosphinyloxyaluminum phthalocyanine, polyhalogenated diphenylphosphinyloxyaluminum phthalocyanine; C.I. I. Purple pigments such as Pigment Violet 23, 29, 32, 50 and the like are included. Among these pigments, C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 15:6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 and the like are preferred.

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. A black pigment may be used alone, or a mixture of the red pigment, the green pigment, the blue pigment, and the like may be used. Examples of black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoint of light shielding rate and image characteristics.

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

The coloring material may contain a pigment derivative as a dispersing aid. As the dye derivative, it is preferable to contain an acidic dye derivative having an acidic group in order to ionically bond with and adsorb to the tertiary amino group and quaternary ammonium base in the block copolymer contained in the dispersant. . This dye derivative has an acidic functional group introduced into the dye skeleton. As the pigment skeleton, a skeleton identical or similar to that of the coloring material constituting the coloring composition, and a skeleton identical or similar to that of the compound that is the raw material of the pigment are preferable. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, and a perylene dye skeleton. A carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable as the acidic group to be introduced into the dye skeleton. A sulfonic acid group is preferred for the convenience of synthesis and for its strong 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, ether, sulfonamide or urethane bond. The amount of the pigment derivative to be used is not particularly limited, but it is preferably 4 parts by mass to 17 parts by mass with respect to 100 parts by mass of the colorant.

The upper limit of the content of the coloring material in the coloring composition, from the viewpoint of brightness, in the total solid content of the coloring composition is usually 80% by mass, preferably 70% by mass, and 60% by mass. is more preferable. Further, the lower limit of the content of the coloring agent in the coloring composition is usually 10% by mass, preferably 20% by mass, 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, which will be described later.

The content of the dispersant for the coloring agent in the coloring composition is preferably 5 parts by weight to 200 parts by weight with respect to 100 parts by weight of the coloring material, preferably 10 parts by weight to 100 parts by weight, 10 parts by weight parts to 80 parts by mass is more preferable.

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

Glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, and propylene. Glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl- 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and the like. Glycol dialkyl ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and the like. Glycol alkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl Ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and the like. Glycol diacetates include ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate and the like. Cyclohexanol acetate etc. are mentioned as alkyl acetates. Ethers include amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether and the like. Ketones include acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxy Methylpentanone and the like can be mentioned. Monohydric or polyhydric alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1-methoxy-2-propanol, methoxymethyl pentanol, glycerin, benzyl alcohol and the like. Examples of aliphatic hydrocarbons include n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane. Alicyclic hydrocarbons include cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl and the like. Aromatic hydrocarbons include benzene, toluene, xylene, cumene and the like. Chain or cyclic esters include amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate. , isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone and the like. Alkoxycarboxylic acids include 3-methoxypropionic acid, 3-ethoxypropionic acid and the like. Examples of halogenated hydrocarbons include butyl chloride and amyl chloride. Methoxymethylpentanone etc. are mentioned as ether ketones. Nitriles include acetonitrile, benzonitrile and the like. The organic solvent should be glycol alkyl ether acetates, glycol monoalkyl ethers, monohydric or polyhydric alcohols, from the viewpoint of dispersibility of the coloring material, solubility of the dispersant, applicability of the coloring composition, etc. is preferred. Only one kind of solvent may be contained in the coloring composition, or plural kinds thereof may be used.

When forming pixels of a color filter by photolithography, the boiling point of the dispersion medium is preferably 100° C. to 200° C. (under a pressure of 1013.25 hPa. Hereinafter, all boiling points are the same.), and 120° C. to 170° C. is preferable. more preferred. Among the above dispersion media, glycol alkyl ether acetates are preferred because they have a good balance of applicability, surface tension, etc., and relatively high solubility of the constituent components in the coloring composition. Glycol alkyl ether acetates may be used alone or in combination with other dispersion media. In this case, it is also preferable to use a dispersion medium having a boiling point of 150° C. or higher. By using a dispersing medium having such a high boiling point together, the coloring composition becomes difficult to dry, and destruction of interrelationships of the coloring composition due to rapid drying can be suppressed. The content of the dispersion medium having a boiling point of 150° C. or higher is preferably 3% by mass to 50% by mass with respect to 100% by mass of the entire dispersion medium. If the content is 3% by mass or more, it is possible to suppress the occurrence of foreign matter defects caused by the deposition and solidification of the coloring material at the tip of the slit nozzle. If it is 50% by mass or less, the drying speed of the coloring composition becomes slow, and problems such as prolonged drying time and pin marks during prebaking can be suppressed in the production of color filters described later. The dispersion medium having a boiling point of 150° C. or higher may be glycol alkyl ether acetates, and in this case, the dispersion medium having a boiling point of 150° C. or higher may not be included separately.

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

In the production of color filters by the inkjet method, the ink emitted from the nozzle is extremely fine, ranging from several pL to several tens of pL. tends to concentrate and dry up. In order to avoid this, it is preferable that the boiling point of the dispersion medium is high. Specifically, it is preferable to include a dispersion medium having a boiling point of 180° C. or higher. More preferably, it contains a dispersion medium having a boiling point of 200° C. or higher, particularly preferably 220° C. or higher. Further, the high-boiling solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass with respect to 100% by mass of the entire dispersion medium contained in the coloring composition The above is most preferable. By making it equal to or higher than the above lower limit, there is a tendency that the effect of preventing the solvent from evaporating from the droplets can be sufficiently exhibited.

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 dispersing medium in the coloring composition is usually 99% by mass. Moreover, the lower limit of the content of the dispersion medium in the coloring composition is usually 70% by mass, preferably 75% by mass, in consideration of the viscosity suitable for application of the coloring composition. The dispersing medium can be used as a solvent for dissolving and removing precipitates formed from the coloring composition.

(binder resin)
The coloring composition of the present invention contains a binder resin (excluding the block copolymer). Thereby, the alkali developability of the coloring composition and the binding property to the substrate can be improved. Although such a binder resin is not particularly limited, it is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group. As the binder resin, for example, for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least a part of the epoxy group of the copolymer has an unsaturated monobasic Alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxy groups generated by the addition reaction, or a resin obtained by adding an acid; a linear alkali-soluble resin containing a carboxy group in the main chain resin; resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of a carboxy group-containing resin; (meth)acrylic resin; epoxy (meth)acrylate resin having a carboxy group; can be used alone or in combination of two or more.

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

In the binder resin, the total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from the (meth)acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably It is 70% by mass or more. In the binder resin, the content of the structure derived from the carboxy group-containing vinyl monomer is preferably 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 preferred, and more preferably 70% by mass or less.

Among these, random copolymers of carboxy group-containing vinyl monomers and (meth)acrylates are preferred. Specific examples of such copolymers include random copolymers of (meth)acrylic acid and butyl (meth)acrylate, random copolymers of (meth)acrylic acid and benzyl (meth)acrylate, (meth) ) Random copolymers of acrylic acid, butyl (meth)acrylate and benzyl (meth)acrylate. From the viewpoint of 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 (meth)acrylate, the content of (meth)acrylic acid is usually 5% to 90% by mass, and 10% to 70% by mass, based on the total monomer components. and more preferably 20% by mass to 70% by mass.

The binder resin may have a radically polymerizable carbon-carbon double bond in its side chain. By having a double bond in the side chain, the photocurability of the colored composition according to the present invention is enhanced, so that resolution and adhesion can be further improved. Examples of methods for introducing radically polymerizable carbon-carbon double bonds to side chains 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 the acidic group of the binder resin.

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

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

The binder resin contained in the coloring composition may be 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 with respect to 100 parts by mass of the coloring material, more preferably 10 parts by mass to 100 parts by mass, 20 parts by mass parts to 80 parts by mass is more preferable.

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

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

Examples of the aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; of aliphatic polyhydroxy compounds. Examples of (meth)acrylates having a hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, di pentaerythritol hexa(meth)acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; pyromellitic anhydride and biphenyltetracarboxylic acid. Tetrabasic acid dianhydrides such as acid dianhydrides and benzophenonetetracarboxylic acid dianhydrides can be mentioned.

In the coloring composition of the present invention, the content of the cross-linking agent is preferably 10 parts by mass to 1,000 parts by mass, particularly preferably 20 parts by mass to 500 parts by mass, based on 100 parts by mass of the coloring material. If the content of the cross-linking agent is too small, there is a possibility that sufficient curability cannot be obtained. On the other hand, if the amount of the cross-linking agent is too large, the colored composition of the present invention will have reduced alkali developability, and scumming, film residue, etc. tend to occur easily on the substrate or on the light-shielding layer in the unexposed area. .

(Photoinitiator)
The coloring composition preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be imparted to the coloring composition. The photopolymerization initiator is a compound that generates active species capable of initiating polymerization of the cross-linking agent upon 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. compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, and the like. A photoinitiator can be used individually or in mixture of 2 or more types.

In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, relative to 100 parts by mass of the cross-linking agent. In this case, if the content of the photopolymerization initiator is too low, curing by exposure may be insufficient. .

(other additives)
In addition to the additives described above, other additives may be added to the coloring composition as long as they do not impair the preferred physical properties of the present invention. Other additives include dispersants other than the block copolymer, sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, Plasticizer, organic carboxylic acid compound, organic carboxylic anhydride, pH adjuster, antioxidant, UV absorber, light stabilizer, preservative, antifungal agent, anti-aggregation agent, adhesion improver, development improver, Storage stabilizers and the like can be mentioned.

Dispersants other than the block copolymer include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, fatty group-modified polyester-based dispersants, and the like.

Sensitizing dyes include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4-diaminobenzophenone, 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-( p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p -diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)1,3,4-thiadiazole, ( p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. is mentioned.

Thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.

Nonionic surfactants include fluorine surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra fluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc.), silicone surfactants, polyoxyethylene surfactants Agents (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythrityl fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc.) mentioned.

Examples of anionic surfactants include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, higher alcohol sulfates, aliphatic Alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer surfactants agents and the like.
Cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like.
Amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, amino acids and the like.

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

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

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

<Method for producing colored composition and color filter>
The colored composition can be prepared by mixing a dispersant (polymerization product), a coloring agent, a dispersion medium, a binder resin, and optionally a cross-linking agent, a photopolymerization initiator, other additives, and the like. For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver, kneader, etc. can be used.

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

The color filter of the present invention comprises a colored layer formed using the coloring composition. Examples of methods for manufacturing color filters include the following methods. Thermosetting resin sheets such as thermoplastic resin sheets such as polyester resin, polyolefin resin, polycarbonate resin and polymethyl methacrylate resin, epoxy resin, unsaturated polyester resin and poly(meth)acrylic resin, various types of glass After applying the coloring composition of the present invention in which a red pigment is dispersed, for example, on a transparent substrate such as the above, prebaking is performed to evaporate the solvent (dispersion medium) to form a coating film. Next, after exposing this coating film through a photomask, it is developed using an alkaline developer (such as an aqueous solution containing an organic solvent or a surfactant and an alkaline compound) to dissolve and remove the unexposed areas of the coating film. do. After that, post-baking is performed to form a pixel array in which a red pixel pattern is arranged in a predetermined arrangement. Next, using each green or blue coloring composition, each coloring composition is applied, pre-baked, exposed, developed and post-baked in the same manner as described above to form a green pixel array and a blue pixel array on the same substrate. Form on top. As a result, a color filter is obtained in which a pixel array of the three primary colors of red, green and blue is arranged on the substrate. However, in the present invention, the order of forming pixels of each color is not limited to the above. A black matrix may be provided on the transparent substrate used for forming the three primary color pixel arrays of red, green and blue.

When the coloring composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.
After forming a protective film on the thus obtained pixel pattern as necessary, a transparent conductive film (such as ITO) 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 can be suitably used for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these specific examples. Various physical properties were measured using the following instruments. Abbreviations have the following meanings.
MMA: methyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate EHMA: 2-ethylhexyl methacrylate MA: methyl acrylate BA: n-butyl acrylate M4EGM: methoxypolyethylene glycol monomethacrylate (the number of added moles of ethylene oxide is 4) (trade name: Blemmer (registered trademark) PME-200, manufactured by NOF Corporation)
MAA: methacrylic acid PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Industries, Plaxel (registered trademark) FM5)
DMAEMA: 2-(dimethylamino)ethyl methacrylate DMAPAAm: N-(3-dimethylaminopropyl)acrylamide BzCl: benzyl chloride BTEE: ethyl-2-methyl-2-n-butyltheranyl-propionate DBDT: dibutyl ditelluride AIBN: 2,2'-azobis(isobutyronitrile)
ADVN: Azobis(2,4-dimethylvaleronitrile)
PMA: propylene glycol monomethyl ether acetate MeOH: methanol

[Evaluation method]
(Polymerization rate)
¹ H-NMR was measured (solvent: deuterated chloroform, internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) spectrometer (manufactured by Bruker, model: AVANCE500 (frequency: 500 MHz)). For the obtained NMR spectrum, the integration ratio of the peaks of the vinyl group derived from the monomer and the peak of the ester side chain derived from the polymer was determined to calculate the polymerization rate of the monomer.

(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). One column SHODEX GPC KF-603 (Φ6.0 mm × 150 mm) (manufactured by Showa Denko), 30 mmol / L lithium bromide -30 mmol / L acetic acid -N-methylpyrrolidone solution to the mobile phase, differential refraction to the detector used the meter. The measurement conditions were a column temperature of 40° C., a sample concentration of 10 mg/mL, a sample injection amount of 10 μL, and a flow rate of 0.2 mL/min. Polystyrene (molecular weight 70,500, 37,900, 19,920, 10,200, 4,290, 2,630, 1,150) is used as a standard substance to create a calibration curve (calibration curve), and the weight average Molecular weight (Mw) and number average molecular weight (Mn) were measured. A molecular weight distribution (PDI=Mw/Mn) was calculated from these measured values.

(amine value)
The amine value is expressed as the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of solid content. A measurement sample was dissolved in tetrahydrofuran, and the resulting solution was neutralized and titrated with a 0.1 mol/L hydrochloric acid/2-propanol solution using a potentiometric titrator (trade name: GT-200, manufactured by Mitsubishi Chemical Corporation). Using the inflection point of the titration pH curve as the titration end point, the amine value (B) was calculated by the following formula.
B = 56.11 x Vs x 0.1 x f/w
B: amine value (mgKOH/g)
Vs: Amount (mL) of 0.1 mol/L hydrochloric acid/2-propanol solution required for titration
f: titer of 0.1 mol/L hydrochloric acid/2-propanol solution w: mass (g) of measurement sample (in terms of solid content)

(acid number)
The acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content. A measurement sample was dissolved in tetrahydrofuran, several drops of phenolphthalein ethanol solution were added as an indicator, and neutralization titration was carried out with a 0.1 mol/L potassium hydroxide/2-propanol solution. The acid value (A) was calculated by the following formula.
A = 56.11 x Vs x 0.1 x f/w
A: Acid value (mgKOH/g)
Vs: amount of 0.1 mol/L potassium hydroxide/2-propanol solution used for titration (mL)
f: Potency of 0.1 mol/L potassium hydroxide/propanol solution w: Mass (g) of measurement sample (in terms of solid content)

(Content of block copolymer)
High-performance liquid chromatography (trade name: HPLC 11 Series, manufactured by Agilent Technologies), column (trade name: L-Column2 ODS 5 μm, 4.6 × 150 mm, manufactured by CERI), column temperature 40 ° C., detector (ELSD PL-ELS2100 , polymer laboratory, evaporator temperature 80 ° C., nebulizer temperature 70 ° C., gas flow rate 1.1 SLM), mobile phase A (acetonitrile: water: trifluoroacetic acid = 80: 20: 0.1 volume ratio), mobile phase B (tetrahydrofuran : trifluoroacetic acid = 100:0.1 volume ratio) at a flow rate of 1 mL/min under a gradient condition of 100% mobile phase A to 100% mobile phase B in 10 minutes. As a sample, 5 μL of a 7 mg/mL acetonitrile:THF:water=4:1:1 (volume ratio) solution was injected. A calibration curve was prepared using separately synthesized unconnected components of each block, and each was quantified. The content of the block copolymer was obtained by subtracting the amount of unconnected components from the total.

(viscosity)
Using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.), the viscosity was measured at 25° C. using a cone rotor (0.8°×R24). In addition, the initial measurement was performed on the colored composition immediately after preparation. After preparation, the storage stability was measured for the colored composition stored at 23°C for 1 week, or for the colored composition stored at 40°C for 1 week.

(Pigment particle size)
5.4 g of PMA was added to 0.6 g of the coloring composition and measured with a particle size distribution meter (FPAR-1000, manufactured by Otsuka Electronics) to obtain the average particle size of the cumulant analysis results. In addition, the initial measurement was performed on the colored composition immediately after preparation. The storage stability was evaluated for the colored composition stored at 40°C for 1 week after preparation.

<Production of block copolymer>
(Manufacturing method No. 1)
39.5 g of MMA previously purged with argon, 19.0 g of BMA, 13.2 g of BzMA, 17.9 g of EHMA, 6.91 g of M4EGM, 6.91 g of MAA, 6.91 g of MAA, BTEE in a 1 L reactor purged with argon and equipped with a stirrer. 43 g, 3.96 g of DBDT, 0.70 g of AIBN, and 69.0 g of PMA were charged and reacted at 54° C. for 19 hours. The polymerization rate was 99%.

To this reaction solution, 46.5 g of DMAEMA and 31.0 g of PMA, which had been replaced with argon in advance, were added and reacted at 54° C. for 22 hours. The polymerization rate was 98%. In addition, the first-stage monomer remaining in the reaction solution was also polymerized, and the polymerization rate of the first-stage monomer remaining in these reaction solutions was 100%.

13.1 g of BzCl previously substituted with argon and 216.0 g of MeOH were added to this reaction solution and reacted at 60° C. for 20 hours.

After completion of the reaction, the reaction solution was diluted with tetrahydrofuran (THF) and poured into heptane under stirring. The precipitated polymer was filtered with suction and dried to obtain a polymerization product no. got 1. The polymerization product has an Mw of 7,599, a PDI of 1.3, an amine value of 67 mgKOH/g, an acid value of 31 mgKOH/g, and an unconnected component in the first stage of polymerization (random polymer having the same composition as the A block ) was 9% by mass, the content of unconnected components in the second stage of polymerization (random polymer having the same composition as block B) was 7% by mass, and the content of the block copolymer was 84% by mass. rice field. The content of each structural unit in the copolymer was calculated from the charging ratio and polymerization rate of the monomers used in the polymerization reaction.

(Manufacturing method No. 2)
163.2 g of MMA previously purged with argon, 78.5 g of BMA, 55.3 g of BzMA, 75.6 g of EHMA, 29.0 g of M4EGM, 28.9 g of MAA, 25.9 g of BTEE in a 3 L reactor purged with argon and equipped with a stirrer. 0 g, 15.5 g of DBDT, 2.7 g of AIBN, and 268.6 g of PMA were charged and reacted at 60° C. for 15 hours. The polymerization rate was 98%.

192.3 g of DMAEMA and 128.0 g of PMA, which had been replaced with argon in advance, were added to this reaction solution and reacted at 60° C. for 7 hours. The polymerization rate was 97%. In addition, the first-stage monomer remaining in the reaction solution was also polymerized, and the polymerization rate of the first-stage monomer remaining in these reaction solutions was 100%.

54.8 g of BzCl previously substituted with argon and 878.9 g of MeOH were added to this reaction solution and reacted at 60° C. for 20 hours.

After completion of the reaction, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was filtered with suction and dried to obtain a polymerization product no. got 2. The polymerization product has an Mw of 7,644, a PDI of 1.3, an amine value of 64 mgKOH/g, an acid value of 29 mgKOH/g, a content of unlinked components in the first stage of polymerization of 21% by mass, and a second stage of polymerization. The content of unconnected components was 9% by mass, and the content of block copolymer was 70% by mass. The content of each structural unit in the copolymer was calculated from the charging ratio and polymerization rate of the monomers used in the polymerization reaction.

(Manufacturing method No. 3)
36.8 g of BMA, 110.4 g of PCL5, 5.99 g of BTEE, 3.69 g of DBDT, 0.7 g of AIBN, and 98.1 g of PMA, which were previously replaced with argon, were charged into a 500 mL reactor equipped with a stirrer and replaced with argon. °C for 23 hours. The polymerization rate was 99%.

To this reaction solution, 46.4 g of DMAEMA and 30.9 g of PMA, which had been replaced with argon in advance, were added and reacted at 54° C. for 21 hours. The polymerization rate was 98%. In addition, the first-stage monomer remaining in the reaction solution was also polymerized, and the polymerization rate of the first-stage monomer remaining in these reaction solutions was 100%.

After completion of the reaction, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was filtered with suction and dried to obtain a polymerization product no. got 3. The polymerization product has an Mw of 15,434, a PDI of 1.5, an amine value of 83 mgKOH/g, a content of unlinked components in the first stage of polymerization of 5% by mass, and an unlinked component in the second stage of polymerization. The percentage was 3% by mass, and the content of the block copolymer was 92% by mass.

(Manufacturing method No. 4)
A stirrer was placed in a 60 mL screw neck test tube and replaced with argon, and then 2.30 g of BMA, 6.90 g of PCL5, 0.375 g of BTEE, 0.231 g of DBDT, 0.04 g of AIBN, and 6.13 g of PMA, which had been replaced with argon in advance, were added. It was prepared and reacted at 65° C. for 29 hours. The polymerization rate was 99%.

To this reaction solution, 2.90 g of DMAEMA and 1.93 g of PMA, which had been replaced with argon in advance, were added and reacted at 65° C. for 16 hours. The polymerization rate was 99%. In addition, the first-stage monomer remaining in the reaction solution was also polymerized, and the polymerization rate of the first-stage monomer remaining in these reaction solutions was 100%.

After completion of the reaction, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was filtered with suction and dried to obtain a polymerization product no. Got 4. The polymerization product has an Mw of 20,363, a PDI of 1.9, an amine value of 85 mgKOH/g, a content of unlinked components in the first stage of polymerization of 18% by mass, and an unlinked component in the second stage of polymerization. The percentage was 8% by weight, and the content of the block copolymer was 74% by weight.

(Manufacturing method No. 5)
53.71 g of MA, 30.08 g of BA, 3.00 g of BTEE, 2.48 g of ADVN, and 56.0 g of ethyl acetate, which had been previously purged with argon, were placed in a 500 mL reactor equipped with a stirrer and purged with argon, and the mixture was heated at 30° C. for 23 hours. reacted. The polymerization rate was 97%.

To this reaction solution, 30.61 g of DMAPAAm and 20.40 g of ethyl acetate, which had been previously replaced with argon, were added and reacted at 30° C. for 48 hours. The polymerization rate was 96%. In addition, the first-stage monomer remaining in the reaction solution was also polymerized, and the polymerization rate of the first-stage monomer remaining in these reaction solutions was 100%.

To this reaction solution, 12.1 g of diethyl sulfate and 63.4 g of MeOH, which had been replaced with argon in advance, were added and reacted at 30° C. for 20 hours. After completion of the reaction, the reaction solution was diluted with tetrahydrofuran (THF) and poured into heptane under stirring. The precipitated polymer was filtered with suction and dried to obtain a polymerization product no. Got 5. The polymerization product has an Mw of 11,936, a PDI of 1.2, an amine value of 52 mgKOH/g, a content of unlinked components in the first stage of polymerization of 3% by mass, and an unlinked component in the second stage of polymerization. The percentage was 2% by weight, and the content of the block copolymer was 95% by weight.

Manufacturing method no. 1, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process are both 54 ° C., and the difference (T _2/1 -Tr) is 11°C. This production method no. The polymerization product obtained in 1 has a high desired block copolymer content of 84% by mass and reduced polymer impurities.

Manufacturing method no. 2, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process are both 60 ° C., and the difference (T _2/1 -Tr) is 5°C. This production method no. The polymerization product obtained in 2 has a low content of the desired block copolymer of 70% by mass and a high content of polymer impurities.

Manufacturing method no. 3, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process are both 54 ° C., and the difference (T _2/1 -Tr) is 11°C. This production method no. The polymerization product obtained in 3 has a desired block copolymer content as high as 92% by mass, and polymer impurities are reduced.

Manufacturing method no. 4, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process are both 65 ° C., and the difference (T _2/1 -Tr) is 0°C. This production method no. The polymerization product obtained in 4 has a low content of the desired block copolymer of 74% by mass and a high content of polymer impurities.

Manufacturing method no. 5, the reaction temperature in the first stage of the polymerization process and the second stage of the polymerization process are both 30 ° C., and the difference (T _2/1 -Tr) is 22°C. This production method no. The polymerized product obtained in 5 has a desired block copolymer content as high as 95% by mass, and polymer impurities are reduced.

<Coloring composition>
C. I. Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals) 12 parts by mass, polymerization product 3.6 parts by mass, binder resin (benzyl methacrylate/methacrylic acid copolymer = 60/40 (mass ratio ), acid value 128 mg KOH / g, weight average molecular weight 9,150) 3.6 parts by mass, PMA 80.8 parts by mass, 0.3 mm zirconia beads 100 parts by mass were added, and a bead mill (trade name: DISPERMAT CA, VMA-GETZMANN GmbH) for 2 hours to fully disperse. After completion of dispersion, the beads were separated by filtration and filtered through a PTFE membrane filter having a pore size of 5 μm to obtain a pigment dispersion (pigment composition).

Coloring composition no. No. 1 uses the polymer product No. 1 as a dispersant. 1 is used. This coloring composition no. 1 has a low viscosity in the initial evaluation, a small average particle size of the pigment, and excellent dispersibility of the pigment. In addition, the viscosity in the storage stability (40° C., 1 week) evaluation is low, and the average particle size of the pigment is almost the same as in the initial evaluation. Therefore, the storage stability of the dispersant is also excellent.

Coloring composition no. 2 contains the polymer product No. 2 as a dispersant. 2 is used. This coloring composition no. In No. 2, the viscosity in the initial evaluation was high, the average particle size of the pigment was large, and the dispersibility of the pigment was poor. In addition, the viscosity in the storage stability (40° C., 1 week) evaluation increased to four times or more of the initial evaluation, and the average particle size of the pigment also increased from the initial evaluation. Therefore, it can be seen that when the content of polymer impurities in the polymerization product used as the dispersant is high, the storage stability is poor.

Coloring composition no. No. 3 uses the polymer product No. 3 as a dispersant. 3 is used. This coloring composition no. 3 has a low viscosity in the initial evaluation, a small average particle size of the pigment, and excellent dispersibility of the pigment. Moreover, coloring composition No. Compared to 4, the viscosity in the storage stability (23° C., 1 week) evaluation is also lower. Therefore, the storage stability of the dispersant is also excellent.

Coloring composition no. No. 4 uses the polymer product No. 4 as a dispersant. 4 is used. This coloring composition no. In No. 4, the resulting pigment dispersion was gelled and the pigment could not be sufficiently dispersed. In the initial evaluation, the viscosity was very high, the average particle size of the pigment was large, and the dispersibility of the pigment was poor.

Coloring composition no. No. 5 uses the polymer product No. 5 as a dispersant. 5 is used. This coloring composition no. 5 has a low viscosity in the initial evaluation, a small average particle size of the pigment, and excellent dispersibility of the pigment. In addition, the viscosity in the storage stability (40° C., 1 week) evaluation is low, and the average particle size of the pigment is almost the same as in the initial evaluation. Therefore, the storage stability of the dispersant is also excellent.

The polymerized product of the present invention can be used as a dispersant for coloring materials in coloring compositions. The coloring composition can be suitably used for color filters. The color filters have high dimensional accuracy and can be suitably used for color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Claims (12)

A polymerization product obtained by polymerizing a monomer composition,
(Meth) containing a block copolymer having an A block having a structural unit derived from an acrylic vinyl monomer and a B block having a structural unit represented by the following general formula (1),
The polymerization product has a molecular weight distribution (PDI) of 2.0 or less, and
A polymerized product, wherein the content of the block copolymer is 75% by mass or more in 100% by mass of the polymerized product.

[In formula (1), R ¹¹ and R ¹² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may combine with each other to form a cyclic structure. X ¹ represents a divalent linking group. ^R13 represents a hydrogen atom or a methyl group. ] The polymerized product of claim 1, wherein the polymerized product has a weight average molecular weight of 5,000 to 40,000. The polymerized product according to claim 1 or 2, wherein the polymerized product has an amine value of 3 mgKOH/g to 180 mgKOH/g. The polymerization product according to any one of claims 1 to 3, wherein the polymerization product is produced by living radical polymerization. The polymerization product according to any one of claims 1 to 4, wherein the mass ratio of A block to B block (A block/B block) in the block copolymer is 50/50 to 95/5. . Polymerization product according to any one of claims 1 to 5, wherein said block copolymer is an AB type diblock copolymer. A dispersant characterized in that it is composed of the polymerization product according to any one of claims 1-6. The dispersant according to claim 7, which is for color filters. A coloring composition comprising the dispersant according to claim 7 or 8, a coloring material, a dispersion medium and a binder resin. A color filter comprising a colored layer formed using the colored composition according to claim 9 . A method for producing a polymerization product according to any one of claims 1 to 6,
A first mixture of an organotellurium compound represented by general formula (3) and an azo polymerization initiator, or an organotellurium compound represented by general formula (3), an azo polymerization initiator, and general formula (4) A block polymerization step of polymerizing a first monomer composition containing a (meth)acrylic vinyl monomer using a second mixture with an organic ditelluride compound represented by
and a B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by the general formula (1) using the first mixture or the second mixture,
In all polymerization steps, the difference (T _1/2 -Tr) between the 10-hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) is 10°C to 60°C. A method for producing a polymerization product characterized by:

[In 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 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, 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 general formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ] 12. The method for producing a polymerization product according to claim 11, wherein the polymerization rate of the monomer composition is 96% or more in all the polymerization steps.