JP7217680B2 - Block copolymers, dispersants, coloring compositions and color filters - Google Patents

Description

The present invention relates to block copolymers, dispersants, coloring compositions and color filters.

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.

On the other hand, 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 increased viscosity of the coloring composition. Therefore, a resin-type dispersant is used. However, when a large amount of the resin-type dispersant is used, heat resistance problems such as a decrease in the contrast ratio of the color filter and a change in hue occur before and after the process accompanied by high heat. Therefore, in Patent Document 1, in order to obtain a coloring composition that achieves both heat resistance and dispersibility, it consists of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. , an AB block copolymer has been proposed as a dispersant (see Patent Document 1 (claim 1, paragraphs 0049 to 0058)).

JP 2012-068559 A

Conventionally, coloring compositions with improved heat resistance have been proposed, but no method has been proposed for improving the heat resistance of the resin type dispersant itself. 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 heat resistance.

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

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２－１）または一般式（２－２）で表される対イオンを示す。
式（２－１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２－２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In Formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. ^R15 represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by general formula (2-1) or general formula (2-2).
In formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

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

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a block copolymer that can be used, for example, as a dispersant and has excellent heat resistance.

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

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２－１）または一般式（２－２）で表される対イオンを示す。
式（２－１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２－２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In Formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. ^R15 represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by general formula (2-1) or general formula (2-2).
In formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

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.

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

In the present invention, "A block" can be 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".

Various constituent components of the block copolymer of the present invention are 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, the heat resistance of the block copolymer can be enhanced while maintaining high affinity with solvents and binder resins.

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 an aromatic group. Acrylate, (meth)acrylate having a polyalkylene glycol structural unit, (meth)acrylate having a hydroxyl group, (meth)acrylate having a lactone-modified hydroxyl group, (meth)acrylate having an alkoxy group, having an oxygen-containing heterocyclic group (Meth)acrylates, (meth)acrylates having an acidic group, (meth)acrylic acid, and the like can be mentioned, and one or more of these can be used in combination.

As the (meth)acrylate having a straight-chain alkyl group, a (meth)acrylate having a straight-chain alkyl group having 1 to 20 carbon atoms in 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. The cyclic alkyl group includes a cyclic alkyl group having a monocyclic structure (eg, cycloalkyl group) and a cyclic alkyl group having a bridged ring structure (eg, adamantyl group, norbornyl group, isobornyl group). 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. Specific examples of (meth)acrylates having a cyclic alkyl group with a bridged ring structure include isobornyl (meth)acrylate, norbornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, and the like. be done.

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, and preferably 80% by mass or less, more preferably 70% by mass or less. , more preferably 60% by mass or less, particularly preferably 50% 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 an aromatic group, (meth)acrylate having a hydroxy group, (meth)acrylate having an alkoxy group, (meth)acrylate having an oxygen-containing heterocyclic group, having an acidic group It is preferable to contain only one or more selected from (meth)acrylates, (meth)acrylic acid, and (meth)acrylates having polyalkylene glycol structural units. 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 60% by mass or less, more preferably 50% 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 an aromatic group, (meth) acrylates having a hydroxy group, (meth) acrylates having an alkoxy group, (meth) acrylates having an oxygen-containing heterocyclic group, acidic groups (meth)acrylates, one or more selected from (meth)acrylic acid, and (meth)acrylates 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 content of structural units derived from a (meth)acrylate having a lactone-modified hydroxy group is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 100% by mass of the A block. It is 20% by mass or more, particularly preferably 30% by mass or more, most preferably 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, further 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 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 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 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 has a structural unit derived from a vinyl monomer having an acidic group (preferably (meth)acrylate or (meth)acrylic acid having an acidic group), thereby increasing the solubility in an alkaline developer and improving the alkaline developability. can be improved. However, if the ratio is high, 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 and preferably 20% by mass or less in 100% by mass of the A block. 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 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 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、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２－１）または一般式（２－２）で表される対イオンを示す。
式（２－１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２－２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In Formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. ^R15 represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by general formula (2-1) or general formula (2-2).
In formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

The chain hydrocarbon groups represented by R ¹¹ to R ¹³ include both linear and branched chains. Examples of substituents possessed by the chain hydrocarbon groups represented by R ¹¹ to R ¹³ include alkoxy groups, benzoyl groups (--COC ₆ H ₅ ), and hydroxy groups. Examples of substituents possessed by the cyclic hydrocarbon groups represented by R ¹¹ to R ¹³ include chain alkyl groups, alkoxy groups, and hydroxy groups.

The groups represented by R ¹¹ to R ¹³ are preferably an optionally substituted alkyl group having 1 to 4 carbon atoms and an optionally substituted aralkyl group having 7 to 16 carbon atoms. , methyl group, ethyl group, propyl group and benzyl group (--CH ₂ C ₆ H ₅ ) are more preferred.

Examples of the cyclic structure formed by combining two or more of the above R ¹¹ to R ¹³ 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 (11-1), (11-2), and (11-3).

〔一般式（１１－１）、（１１－２）、（１１－３）において、Ｒ¹⁶は、Ｒ¹¹～Ｒ¹³のいずれかである。Ｒ¹⁷は、炭素数１～６のアルキル基を示す。ｌは０～５の整数を表す。ｍは０～４の整数を表す。ｎは０～４の整数を表す。ｌが２～５、ｍが２～４、ｎが２～４の場合、複数存在するＲ¹⁷は、それぞれ同一でも異なっていてもよい。〕

[In general formulas (11-1), (11-2) and (11-3), R ¹⁶ is any one of R ¹¹ to R ¹³ . R ¹⁷ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4; n represents an integer of 0 to 4; When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ¹⁷ may be the same or different. ]

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

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

Aromatic groups represented by R ²¹ and R ²² include aryl groups, alkylaryl groups, aralkyl groups, aryloxy groups, aryloxyalkyl groups, alkylaryloxy groups, aralkyloxy groups and the like, and have 6 carbon atoms. ~12 aromatic groups are preferred. Specific examples include phenyl group, benzyl group, tolyl group, xylyl group, mesityl group, naphthalene group and the like.

Sulfate ions represented by the formula (2-1) include alkyl sulfate ions such as methyl sulfate, ethyl sulfate, propyl sulfate, and butyl sulfate; aromatics such as phenyl sulfate, benzyl sulfate, and tolyl sulfate ions; group sulfate ions; and the like.

Examples of the sulfonate ion represented by formula (2-2) include alkylsulfonate ions such as methanesulfonate ion, ethanesulfonate ion, propanesulfonate ion, and butanesulfonate ion; benzenesulfonate ion, toluenesulfonate ion; ions, aromatic sulfonate ions such as phenylmethanesulfonic acid; and the like.

Specific examples of vinyl monomers capable of forming the structural unit represented by general formula (1) include (meth)acryloyloxyethyltrimethylammonium methylsulfate, (meth)acryloyloxypropyltrimethylammonium methylsulfate, ( meth) Acryloyloxybutyltrimethylammonium・methylsulfate, (meth)acryloyloxyethyldimethylethylammonium・ethylsulfate, (meth)acryloyloxypropyldimethylethylammonium・ethylsulfate, (meth)acryloyloxybutyldimethylethylammonium・Ethyl sulfate, (meth) acryloyloxyethyltrimethylammonium/toluene-4-sulfonate, (meth) acryloyloxypropyltrimethylammonium/toluene-4-sulfonate, (meth) acryloyloxybutyltrimethylammonium/toluene-4-sulfonate, etc. can be mentioned.

The content of the structural unit represented by general formula (1) is preferably 5% by mass or more, preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more in 100% by mass of the B block. , preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and particularly preferably 70% by 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.

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

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

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

〔式（３）において、Ｒ³¹およびＲ³²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ³¹およびＲ³²は互いに結合して環状構造を形成していてもよい。Ｒ³³は、鎖状の２価の炭化水素基を示す。Ｒ³⁴は、水素原子またはメチル基を示す。〕

[In Formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a chain divalent hydrocarbon group. ^R34 represents a hydrogen atom or a methyl group. ]

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

The group represented by R ³¹ or R ³² 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.

Examples of the cyclic structure formed by combining R ³¹ or R ³² 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 (31-1), (31-2) and (31-3).

〔一般式（３１－１）、（３１－２）、（３１－３）において、Ｒ³⁵は、炭素数１～６のアルキル基を示す。ｌは０～５の整数を表す。ｍは０～４の整数を表す。ｎは０～４の整数を表す。ｌが２～５、ｍが２～４、ｎが２～４の場合、複数存在するＲ³⁵は、それぞれ同一でも異なっていてもよい。〕

[In general formulas (31-1), (31-2) and (31-3), R ³⁵ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4; n represents an integer of 0 to 4; When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R ³⁵ may be the same or different. ]

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

The content of the structural unit represented by general formula (3) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass in 100% by mass of the B block. % by mass or more, preferably 95% by mass or less, more preferably 70% by mass or less, even more preferably 65% by mass or less, and particularly preferably 40% by mass or less. It is believed that by setting the content of the structural unit represented by the general formula (3) within this range, it has 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 (3), 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 (3) in block B is 80% by mass or more. is preferred, more preferably 90% by mass or more, and still more preferably 95% by mass or more. The mass ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (3) in the B block (structural unit represented by the formula (1) / represented by the formula (3) is preferably 30/70 or more, more preferably 35/65 or more, still more preferably 40/60 or more, preferably 90/10 or less, more preferably 85/15 or less, further preferably 80/20 or less.

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 of the present invention 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, from the viewpoint of handleability during processing and physical properties of the composition, AB type diblock copolymers or ABA type triblock copolymers are preferred, and heat resistance and alkali development are preferred. AB type diblock copolymers are more preferred from the viewpoint of their properties. In the case of an ABA type triblock copolymer, the two A blocks located at both ends may be the same or different.

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

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, both dispersibility and alkali developability when used as a dispersant can be achieved in a well-balanced manner.

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

The molecular weight of the block copolymer is measured by a gel permeation chromatography (hereinafter referred to as "GPC") method. The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 6,000 or more. 000 or less, more preferably 30,000 or less, still more preferably 25,000 or less, and particularly 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 distribution (PDI) of the block copolymer is preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.6 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer)/(number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the width of the molecular weight distribution, the more uniform the molecular weight of the copolymer. When the value is 1.0, the narrowest molecular weight distribution. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.2, it includes those with small molecular weights and those with large molecular weights.

The amine value of the block copolymer is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, from the viewpoint of adsorption to the coloring material and coloring material dispersibility, It is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, still more preferably 100 mgKOH/g or less.

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

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

(Method for producing block copolymer)
As a method for producing the block copolymer, the A block is first produced by the polymerization reaction of the vinyl monomer, and the B block is polymerized on the A block; A method of polymerizing block monomers; A method of separately preparing A block and B block and then coupling A block and B block; Polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by Method; Polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by formula (3), polymerizing the A block monomer to this polymer, ) A method of quaternizing a part of the tertiary amine structure of the structural unit represented by A block and a block having a structural unit represented by formula (3) are separately produced, After ringing, a method of quaternizing part of the tertiary amine structure of the structural unit represented by formula (3) in the resulting polymer.

The block copolymer of the present invention is obtained by quaternizing a block copolymer having a structural unit represented by formula (3) with an alkyl halide or the like, and then converting the halogen anion into a sulfate ion and/or a sulfonate ion. It can also be obtained by exchanging. However, halogen tends to remain as an impurity in the block copolymer obtained by such a method. Therefore, the block copolymer of the present invention is a block copolymer having a first block and a second block, wherein the first block contains a structural unit derived from a (meth)acrylic vinyl monomer, and , the content of the structural unit represented by the general formula (3) in the first block is less than 5% by mass, and the content of the structural unit represented by the general formula (3) in the second block is 5 After synthesizing a block copolymer having a mass % or more, at least a part of the tertiary amine structure of the structural unit represented by formula (3) in the obtained block copolymer is replaced with a sulfate compound and / or Those obtained by quaternization with a sulfonic acid compound are preferred. By using a sulfuric acid compound and/or a sulfonic acid compound as a quaternizing agent, a halogen-free block copolymer can be obtained.

Although the polymerization method is not particularly limited, living radical polymerization is preferred. That is, the block copolymer is preferably polymerized by living radical polymerization. In the conventional radical polymerization method, not only initiation reaction and propagation reaction but also termination reaction and chain transfer reaction cause deactivation of propagating terminal, 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); There is a method such as a 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 (4).
(b) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (4) and an azo polymerization initiator.
(c) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (4) and an organic ditelluride compound represented by general formula (5).
(d) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by general formula (4), an azo polymerization initiator, and an organic ditelluride compound represented by general formula (5).

〔一般式（４）において、Ｒ⁴¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を示す。Ｒ⁴²およびＲ⁴³は、それぞれ独立に、水素原子または炭素数１～８のアルキル基を示す。Ｒ⁴⁴は、炭素数１～８のアルキル基、アリール基、置換アリール基、芳香族ヘテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を示す。
一般式（５）において、Ｒ⁴¹は、炭素数１～８のアルキル基、アリール基または芳香族ヘテロ環基を示す。〕

[In general formula (4), R ⁴¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R ⁴² and R ⁴³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ⁴⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In general formula (5), R ⁴¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

The group represented by R ⁴¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and 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 ⁴² and R ⁴³ 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 ⁴⁴ 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 substituents of the aryl group having the above-mentioned substituents include halogen atoms, hydroxy groups, alkoxy groups, amino groups, nitro groups, cyano groups, and carbonyl-containing groups represented by —COR ⁴¹¹ (R ⁴¹¹ 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 ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
The oxycarbonyl group is preferably a group represented by --COOR ⁴³¹ (R ⁴³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group), 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-pentyloxycarbonyl group, phenoxycarbonyl group and the like. Preferred oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl groups.
The allyl group includes -CR ⁴⁴¹ R ⁴⁴² -CR ⁴⁴³ =CR ⁴⁴⁴ R ⁴⁴⁵ (R ⁴⁴¹ and R ⁴⁴² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴³ , R ⁴⁴⁴ and R ⁴⁴⁵ are , 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 ⁴⁵¹ R ⁴⁵² —C≡CR ⁴⁵³ (R ⁴⁵¹ and R ⁴⁵² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁵³ is a hydrogen atom 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 (4) 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 (5) 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), 2,2′-azobis(2-methylbutyronitrile) (AMBN), 2,2′-azobis(2,4-dimethylvaleronitrile) ) (ADVN), 1,1′-azobis(1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis(4-cyanovaleric acid ) (ACVA), 1,1′-azobis(1-acetoxy-1-phenylethane), 2,2′-azobis(2-methylbutyramide), 2,2′-azobis(4-methoxy-2,4 -dimethylvaleronitrile) (V-70), 2,2′-azobis(2-methylamidinopropane) dihydrochloride, 2,2′-azobis[2-(2-imidazolin-2-yl)propane], 2 , 2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis(2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2 , 2′-azobis(N-butyl-2-methylpropionamide) or 2,2′-azobis(N-cyclohexyl-2-methylpropionamide).

In the polymerization step, in a vessel purged with an inert gas, the vinyl monomer and the organic tellurium compound of general formula (4) 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 (5) is 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 organotellurium compound of general formula (4).

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

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

When the organic tellurium compound of general formula (4) in (d), the organic ditelluride compound of general formula (5), and the azo polymerization initiator are used in combination, general formula (4) per 1 mol of the organic tellurium compound The organic ditelluride compound of formula (5) 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 (4).

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, still more preferably 0.1 ml or more, and 50 ml or less per 1 g of the vinyl monomer. It is preferably 10 ml or less, more preferably 1 ml or less.

The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the 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 ⁴¹ (wherein R ⁴¹ is the same as above) derived from the tellurium compound, and is deactivated by an operation in air after the completion of the polymerization reaction. However, 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 (3) is quaternized, the quaternizing agent may be a sulfuric acid compound represented by formula (6-1), or a sulfuric acid compound represented by formula (6-2). and sulfonic acid compounds.

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

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

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

Aromatic groups represented by R ²¹ to R ²⁴ include aryl groups, alkylaryl groups, aralkyl groups, aryloxy groups, aryloxyalkyl groups, alkylaryloxy groups, aralkyloxy groups and the like, and have 6 carbon atoms. ~12 aromatic ring groups are preferred. Specific examples include phenyl group, benzyl group, tolyl group, xylyl group, mesityl group, naphthalene group and the like.

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

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

As a method for quaternizing a part of the tertiary amine structure of the structural unit represented by formula (3) 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 (3), 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 20 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.

<Dispersant>
The dispersant of the present invention contains the block copolymer as a main component (50% by mass or more), preferably contains 75% by mass or more of the block copolymer, more preferably the above Consists only of block copolymers. In the block copolymer, for example, the tertiary amino group and quaternary ammonium base in the structure (B block) are strongly bonded to the acidic group of the acidic coloring agent or the coloring agent treated with an acidic group-containing dye derivative. However, it is believed that the B block 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. Since the coloring composition using the dispersant of the present invention has alkali developability, it can be suitably used as a dispersant for color filters.

<Coloring composition>
The coloring composition of the present invention contains the 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. Green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, 63; 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 colored resin composition. % or more 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 part of the epoxy groups of this copolymer have an unsaturated monobasic acid or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxy groups generated by the addition reaction; a linear alkali-soluble resin having a carboxy group in the main chain; A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of a carboxy group-containing resin; (meth) acrylic resin; epoxy (meth) acrylate resin having a carboxy group; Alternatively, two or more types can be mixed and used.

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 5 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 (block copolymer), 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 or kneader can be used. The coloring composition is preferably filtered after mixing.

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

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 EHMA: 2-ethylhexyl methacrylate M9EGM: methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide: 9) (trade name: Blemmer (registered trademark) PME-400, manufactured by NOF Corporation)
M4EGM: methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide: 4) (trade name: Blemmer (registered trademark) PME-200, manufactured by NOF Corporation)
PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd., Plaxel (registered trademark) FM5)
MAA: methacrylic acid DMAEMA: 2-(dimethylamino)ethyl methacrylate DMAPMAm: N-(3-dimethylaminopropyl) methacrylamide BTEE: ethyl-2-methyl-2-n-butyltheranyl-propionate DBDT: dibutyl ditelluride AIBN : 2,2'-azobis(isobutyronitrile)
ADVN: Azobis(2,4-dimethylvaleronitrile)
Me ₂ SO ₄ : dimethyl sulfate MePTSA: methyl p-toluenesulfonate BzCl: benzyl chloride PMA: propylene glycol monomethyl ether acetate MP: 1-methoxy-2-propanol

(Polymerization rate)
¹ H-NMR was measured (solvent: deuterated chloroform, internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) 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 KF-603 (Φ6.0mm × 150mm) (manufactured by SHODEX), 30mmol / L lithium bromide -30mmol / L acetic acid -N-methylpyrrolidone solution to the mobile phase, a differential refractometer to the detector used. 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-06, 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 a phenolphthalein ethanol solution were added as an indicator, and neutralization titration was carried out with a 0.1 mol/L potassium hydroxide/ethanol 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 (mL) of 0.1 mol/L potassium hydroxide/ethanol solution required for titration
f: Potency of 0.1 mol/L potassium hydroxide/ethanol solution w: Mass (g) of measurement sample (in terms of solid content)

(Halogen anion content)
Sample preparation was performed as follows. About 100 mg of the reaction solution after the quaternization step was charged into a combustion furnace (trade name: AQF-2100H, manufactured by Mitsubishi Chemical Analytic Tech). The heater of the combustion furnace was 900° C. (inside), the gas flow rate was 200 mL/min of argon, 400 mL/min of oxygen, 100 mL/min of argon for humidification, and the residence time of the combustion furnace was 15 minutes. The exhaust gas was captured with a collector (trade name: AU-250, manufactured by Mitsubishi Chemical Analytic Tech). Ultrapure water was used as the absorption liquid, and 35 mL of the obtained water absorption liquid was diluted to 50 mL using ultrapure water to prepare a sample solution.
The halogen anion content was measured using ion chromatography (trade name: DIONEX ICS-1600, manufactured by Thermo Scientific). Ion Pac AS-12A (manufactured by DIONEX) was used as the column, and an eluent for anion analysis (trade name: AS12A, manufactured by DIONEX) was used as the eluent. The measurement conditions were a sample injection volume of 25 μL and a flow rate of 1.5 mL/min. A calibration curve (calibration curve) was created using standard solutions with chloride anion concentrations of 0, 5 ppm, 1 ppm, and 2 ppm as standard substances, and the chloride anion concentration was calculated.

(heating weight loss temperature)
It was measured using a simultaneous thermogravimetric/differential thermal analyzer (TG-DTA) (TG/DTA6300, manufactured by HITACHI). The measurement sample was dried under reduced pressure at a temperature of 130° C. for 1 hour before measurement. The measurement conditions were a sample mass of about 10 mg, an air flow rate of 200 ml/min, a temperature increase rate of 10°C/min, and a measurement temperature range of 40°C to 600°C. The temperature at which the mass of the sample decreased by 10% was read from the obtained TG curve, and this temperature was defined as the heating weight loss temperature.

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

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

<Production of copolymer before quaternization>
(No. 1)
MMA (99.9 g), BMA (64.8 g), EHMA (59.5 g), M9EGM (21.6 g), AIBN (0.74 g), PMA (163 g) were placed in a flask equipped with an argon gas inlet tube and stirrer. .8 g) was charged, and after purging with argon, BTEE (7.09 g) and DBDT (2.50 g) were added and reacted at 60° C. for 16 hours to polymerize the first block. The polymerization rate was 98%.

A mixed solution of DMAEMA (87.8 g), AIBN (0.62 g), and PMA (58.5 g) previously replaced with argon was added to the reaction solution and reacted at 60° C. for 20 hours to polymerize the second block. The polymerization rate of DMAEMA was 99%. In addition, the monomer for the first block remaining in the reaction solution was also polymerized and incorporated into the second block. The polymerization rate of the first block monomer remaining in these reaction solutions was 100%. The content of each structural unit in the copolymer was calculated from the charging ratio and polymerization rate of the monomers used in the polymerization reaction.

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

(No.2-5)
Copolymer No. before quaternization. Copolymer No. 1 before quaternization was prepared in the same manner as in the production method of No. 1. 2 to 5 were produced. Table 1 shows raw material monomers, organic tellurium compounds, organic ditelluride compounds, azo polymerization initiators, solvents, reaction conditions, and polymerization rates used. 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.

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

(No. 7)
Copolymer No. before quaternization except that DMAPMAm was changed to DMAEMA. Copolymer No. 6 before quaternization was prepared in the same manner as in the production method of No. 6. got 7. The non-volatile content was 35.4%.

<Copolymer quaternization step>
A PMA solution or a PMA/MP solution was prepared by dissolving the pre-quaternized copolymer in PMA or a PMA/MP mixed solvent (PMA:MP=1:1 (mass ratio)). The resulting PMA solution or PMA/MP solution of the pre-quaternized copolymer was placed in an eggplant flask. To this solution, dimethyl sulfate (reagent manufactured by Tokyo Kasei), methyl p-toluenesulfonate (reagent manufactured by Tokyo Kasei) or benzyl chloride was added dropwise at room temperature while stirring. After that, the mixture was stirred at 60° C. and reacted. This was cooled to obtain a quaternized block copolymer solution. Tables 3 and 4 show the quaternizing agent, solvent, and reaction conditions used in the quaternization step. Tables 5 and 6 show the composition, Mw, PDI, amine value and acid value of the quaternized copolymer.

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

Copolymer no. 13 and 14 are random copolymers and the counterions of the quaternary ammonium bases are sulfate ions. Copolymer No. 1 using the same monomers. 1 and copolymer no. 14, copolymer No. 1, which is a block copolymer. It can be seen that No. 1 has a higher heating weight loss temperature and is superior in heat resistance.

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

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

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

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

Coloring composition no. Coloring compositions for color filters using No. 1 to No. 7 use copolymer No. 1 as a dispersant. Contains 1-7. These color filter coloring compositions had a low viscosity even after one week and were excellent in alkali developability. In particular, as a dispersing agent, copolymer No. 1 having an acidic group in the A block is used. Coloring compositions for color filters using 2 and 3 were even more excellent in alkali developability in spite of their low quaternization rate.

Coloring composition no. Coloring compositions for color filters using No. 8 to No. 12 use copolymer No. 1 as a dispersant. Contains 8-12. These color filter coloring compositions have a low viscosity even after one week. These coloring compositions for color filters are copolymer Nos. Since the heat resistance of Nos. 8 to 12 is low, the obtained color filter is considered to have low heat resistance.

Coloring composition no. Coloring compositions for color filters using No. 13 and No. 14 use copolymer No. 1 as a dispersant. Contains 13 or 14. These color filter coloring compositions gelled one week after preparation. Therefore, copolymer no. 13 and 14 are inferior in dispersion stability.

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

〔式（１）において、Ｒ¹¹、Ｒ¹²およびＲ¹³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹、Ｒ¹²およびＲ¹³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｒ¹⁴は、鎖状の２価の炭化水素基を示す。Ｒ¹⁵は、水素原子またはメチル基を示す。Ｚ^-は、一般式（２－１）または一般式（２－２）で表される対イオンを示す。
式（２－１）中、Ｒ²¹は、アルキル基もしくは芳香族基を示す。
式（２－２）中、Ｒ²²は、アルキル基もしくは芳香族基を示す。〕

[In Formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a chain divalent hydrocarbon group. ^R15 represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by general formula (2-1) or general formula (2-2).
In formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

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

〔式（３）において、Ｒ³¹およびＲ³²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ³¹およびＲ³²は互いに結合して環状構造を形成していてもよい。Ｒ³³は、鎖状の２価の炭化水素基を示す。Ｒ³⁴は、水素原子またはメチル基を示す。〕

[In Formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a chain divalent hydrocarbon group. ^R34 represents a hydrogen atom or a methyl group. ]

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

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

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

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

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

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

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

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

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

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

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

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

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

(Embodiment 12)
A block copolymer according to any one of embodiments 1 to 11, wherein the block copolymer has an amine value of 10 mg KOH/g to 200 mg KOH/g.

(Embodiment 13)
13. The block copolymer according to any one of embodiments 1-12, wherein the block copolymer has an acid value of 5 mg KOH/g to 50 mg KOH/g.

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

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

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

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

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

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

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

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

The block copolymer of the present invention can be used as a dispersing agent 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 (15)

A dispersant containing a block copolymer,
The block copolymer is an AB type diblock copolymer having an A block and a B block,
The mass ratio of the A block and the B block (A block/B block) in the block copolymer is 50/50 to 95/5,
The A block contains a structural unit derived from a (meth)acrylic vinyl monomer, and the content of the structural unit derived from the (meth)acrylic vinyl monomer is 80% by mass or more in 100% by mass of the A block. and
The A block contains a structural unit derived from a (meth) acrylate having a polyalkylene glycol structural unit and/or a (meth) acrylate having a lactone-modified hydroxy group, and has a polyalkylene glycol structural unit ( The total content of structural units derived from meth)acrylate and structural units derived from (meth)acrylate having a lactone-modified hydroxy group is 5% by mass to 80% by mass in 100% by mass of the A block,
The content of the structural unit represented by the following general formula (1) in the A block is less than 5% by mass,
The content of the structural unit represented by the following general formula (1) in the B block is 5% by mass or more ,
The B block further comprises a structural unit represented by the following general formula (3),
The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3) in the B block is 80% by mass or more,
A dispersant, wherein the block copolymer has a weight average molecular weight (Mw) of 3,000 to 40,000 .

[In Formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may combine with each other to form a cyclic structure. R ¹⁴ represents a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group or heptamethylene group . ^R15 represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by general formula (2-1) or general formula (2-2).
In formula (2-1), R ²¹ represents an alkyl group or an aromatic group.
In formula (2-2), R ²² represents an alkyl group or an aromatic group. ]

[In Formula (3), R ³¹ and R ³² each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R ³¹ and R ³² may combine with each other to form a cyclic structure. R ³³ represents a chain divalent hydrocarbon group. R34 ^represents a hydrogen atom or a methyl group. ] The dispersant according to claim 1 , wherein the content of the structural unit represented by formula (1) is 5% by mass to 90% by mass in 100% by mass of the B block. 3. The dispersant according to claim 1 , wherein the content of the structural unit represented by formula (3) is 10% by mass to 95% by mass in 100% by mass of the B block. The (meth)acrylic vinyl monomer includes (meth)acrylates having a chain alkyl group, (meth)acrylates having a cyclic alkyl group, (meth)acrylates having an aromatic group, and (meth)acrylates having a polyalkylene glycol structural unit. ) acrylates, (meth) acrylates having a hydroxy group, (meth) acrylates having a lactone-modified hydroxy group, (meth) acrylates having an alkoxy group, (meth) acrylates having an oxygen-containing heterocyclic group, (meth) acrylates having an acidic group ) The dispersant according to any one of claims 1 to 3 , which is at least one monomer selected from the group consisting of acrylate and (meth)acrylic acid. The dispersant according to any one of claims 1 to 4 , wherein the block copolymer has an amine value of 10 mgKOH/g to 200 mgKOH/g. The dispersant according to any one of claims 1 to 5 , wherein the block copolymer has an amine value of 55.3 mgKOH/g to 200 mgKOH/g. The dispersant according to any one of claims 1 to 6 , wherein the block copolymer has a molecular weight distribution (PDI) of 2.2 or less. The dispersant according to any one of claims 1 to 7 , wherein the block copolymer is polymerized by living radical polymerization. The (meth)acrylic vinyl monomer is a (meth)acrylate having a hydroxyl group, a (meth)acrylate having a lactone-modified hydroxyl group, a (meth)acrylate having an oxygen-containing heterocyclic group, and a (meth)acrylate having an acidic group. and (meth)acrylic acid . The (meth)acrylic vinyl monomer has a (meth)acrylate having a lactone-modified hydroxy group,
Any one of claims 1 to 9 , wherein the content of the structural unit derived from the (meth)acrylate having a lactone-modified hydroxy group is 5% by mass or more and 90% by mass or less in 100% by mass of the A block. dispersant according to the paragraph. The A block has a structural unit derived from a vinyl monomer having an acidic group,
The content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more and 20% by mass or less in 100% by mass of the A block, according to any one of claims 1 to 10 . Dispersant . The dispersant according to any one of claims 1 to 11, wherein the block copolymer has a halogen anion content of 10 ppm or less . The dispersant according to any one of claims 1 to 12, which is for color filters. A coloring composition comprising the dispersant according to any one of claims 1 to 13 , 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 14 .