WO2019107020A1

WO2019107020A1 - Block copolymer, dispersant, coloring composition, and color filter

Info

Publication number: WO2019107020A1
Application number: PCT/JP2018/039414
Authority: WO
Inventors: 石飛宏幸; 清水達彦
Original assignee: 大塚化学株式会社
Priority date: 2017-11-29
Filing date: 2018-10-24
Publication date: 2019-06-06
Also published as: JPWO2019107020A1; CN111247182B; CN111247182A; JP6640436B2; TW201925253A; KR20200083457A; JP7217680B2; JP2019218547A

Abstract

[Problem] To provide a block copolymer which has excellent heat resistance and can be used as a dispersant. [Solution] The present invention provides a block copolymer having block A and block B, wherein block A contains a structural unit derived from a (meth)acrylic vinyl monomer, the content of a structural unit represented by general formula (1) in block A is less than 5 mass%, and the content of a structural unit represented by general formula (1) in block B is at least 5 mass%. [In formula (1), R11-R13 represent hydrocarbons. R11-R13 may form cyclic structures. R14 represents a divalent hydrocarbon. R15 represents a hydrogen atom or an ethyl group. Z- represents a counter ion represented by general formula (2-1) or (2-2). In formulae (2-1) and (2-2), R21 and R22 represent alkyl groups or aromatic groups.]

Description

Block copolymer, dispersant, coloring composition and color filter

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

Coloring compositions obtained by mixing colorants (pigments, dyes, etc.), dispersants, dispersion media (solvents) and dispersing colorants are used in a wide range of fields such as color filters for liquid crystal displays etc. . For example, in a color filter, in order to apply a coloring material to a substrate, a coating film made of a coloring composition is formed on the substrate, exposed through a photomask having a desired pattern shape, and alkaline development is performed. .

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

On the other hand, the coloring composition is required to be excellent in various characteristics such as sharpness and high transparency, and the coloring of the coloring material is carried out. When the coloring material becomes fine particles, the surface energy is increased to cause aggregation of the coloring material, the storage stability is poor, and the viscosity of the coloring composition is increased, so that the structure design is easy for the dispersant of the coloring composition. Therefore, resin type dispersants are used. However, when many resin-type dispersants are used, the heat resistance such as the decrease in the contrast ratio of the color filter and the change in the hue becomes a problem before and after the process involving high heat. Then, in patent document 1, in order to obtain the coloring composition which made heat resistance and dispersibility make compatible, it consists of A block which has a quaternary ammonium base in a side chain, and B block which does not have a quaternary ammonium base. It has been proposed to use an AB block copolymer as a dispersant (see Patent Document 1 (claim 1, paragraphs 0049 to 0058)).

JP, 2012-068559, A

Conventionally, a coloring composition having improved heat resistance has been proposed, but no method for improving the heat resistance of the resin-type dispersant itself has been proposed. The present invention has been made in view of the above circumstances, and an object thereof is to provide a block copolymer which can be used, for example, as a dispersant and has excellent heat resistance.

The block copolymer of the present invention which has been able to solve the above problems has an A block and a B block, and 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 mass % Or more.

[In formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a linear or cyclic hydrocarbon group which may have a substituent. Two or more of R ¹¹ , R ¹² and R ¹³ may be bonded to each other to form a cyclic structure. R ¹⁴ represents a chain-like divalent hydrocarbon group. R ¹⁵ represents a hydrogen atom or a methyl group. Z ⁻ represents a counter ion represented by the general formula (2-1) or the 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 the general formula (1) and a B block having a high content of structural units represented by the 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 of the structural unit represented by the general formula (1) is a sulfate ion or a sulfonate ion. Therefore, the block copolymer of the present invention is also excellent in heat resistance.

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

The block copolymer of the present invention has an A block and a B block, and the A block contains a structural unit derived from a (meth) acrylic vinyl monomer, and the following general formula (1) in the A block: The content of the structural unit represented by the above 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. .

Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiments are merely illustrative. The present invention is not at all 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" refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from vinyl monomer” refers to a structural unit in which a radical polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to form a carbon-carbon single bond. "(Meth) acrylic" refers to "at least one of acrylic and methacrylic". "(Meth) acrylate" refers to "at least one of acrylate and methacrylate". "(Meth) acryloyl" refers to "at least one of acryloyl and metachloro".

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

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

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

The (meth) acrylic vinyl monomer is a (meth) acrylate having a linear alkyl group (a linear alkyl group or a branched alkyl group), a (meth) acrylate having a cyclic alkyl group, and an aromatic group (meth) Acrylate, (meth) acrylate having a polyalkylene glycol structural unit, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone modified hydroxy group, (meth) acrylate having an alkoxy group, having an oxygen-containing heterocyclic group The (meth) acrylate, the (meth) acrylate which has an acidic group, (meth) acrylic acid etc. can be mentioned, It can be used combining 1 type, or 2 or more types out of these.

The (meth) acrylate having a linear alkyl group is preferably a linear alkyl group having from 1 to 20 carbon atoms (meth) acrylate having a linear alkyl group, and the linear alkyl group has from 1 to 20 carbon atoms. More preferred is a (meth) acrylate having a linear alkyl group of 10. Examples of the (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, Examples include n-octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate and the like.

The (meth) acrylate having a branched alkyl group is preferably a (meth) acrylate having a branched alkyl group in which the carbon number of the branched alkyl group is 1 to 20, and the carbon number of the branched alkyl group is 1 to 20 (Meth) acrylates having a branched alkyl group of 10 are preferred. As the (meth) acrylate having a branched alkyl group, 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 can be mentioned.

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

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

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

Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6- Examples thereof include hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (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 having a caprolactone added are preferable. The addition amount of caprolactone is preferably 1 mol to 10 mol, and more preferably 1 mol to 5 mol. As the (meth) acrylate having a lactone modified hydroxy group, 1 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 2 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate The caprolactone 3 mol adduct of 2-hydroxy ethyl (meth) acrylate, the caprolactone 5 mol adduct of 2-hydroxyethyl (meth) acrylate, the caprolactone 10 mol adduct of 2-hydroxyethyl (meth) acrylate, etc. are preferred. .

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

The (meth) acrylate having an oxygen-containing heterocyclic group is preferably a (meth) acrylate having a 4- to 6-membered oxygen-containing heterocyclic group. Specific examples of the (meth) acrylate having an oxygen-containing heterocyclic group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (3-ethyl oxetan-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 carboxy group (—COOH), sulfonic acid group (—SO ₃ H), phosphoric acid group (—OPO ₃ H ₂ ), phosphonic acid group (—PO ₃ H ₂ ), phosphinic acid group (— PO ₂ H ₂₎ can be mentioned. As the (meth) acrylate having an acidic group, a (meth) acrylate having a carboxy group such as a monomer obtained by reacting an hydroxy anhydride (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 these monomers are used, the total content of structural units derived from (meth) acrylate having a polyalkylene glycol structural unit in A block and structural units derived from (meth) acrylate having a lactone modified hydroxy group is In 100% by mass of the A block, 5% by mass or more is preferable, more preferably 10% by mass or more, further preferably 20% by mass or more, and 80% by mass or less is preferable, more preferably 70% by mass or less More preferably, it is 60% by mass or less, particularly preferably 50% by mass or less.

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

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

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

As a structural unit derived from the (meth) acrylate which has the said polyalkylene glycol structural unit, the structural unit represented, for example by following General formula (7) can be mentioned.

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

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

As a structural unit derived from the (meth) acrylate which has the said lactone modified | denatured hydroxy group, the structural unit represented, for example by following General formula (8) can be mentioned.

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

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

In the block A, the content of structural units represented by the general formula (1) described later is less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less, and in the general formula (1) It is further preferred not to contain the structural units represented. The lower the content of the structural unit represented by the general formula (1) in the A block, the better the dispersion performance of the colorant.

The said A block may have other structural units other than the structural unit derived from a (meth) acrylic-type vinyl monomer. Other structural units that can be included in the A block are particularly limited as long as they are formed of a (meth) acrylic vinyl monomer and a vinyl monomer copolymerizable with both of the vinyl monomers forming the B block described later. Absent. The vinyl monomers capable of forming other structural units of the A block may be used alone or in combination of two or more.

Specific examples of the vinyl monomer which can form another structural unit of A block include α-olefin, aromatic vinyl monomer, vinyl monomer containing a heterocycle, vinylamide, vinyl carboxylate, dienes and the like. These vinyl monomers may have a hydroxy group or an epoxy group.

Examples of α-olefins include 1-hexene, 1-octene, 1-decene and the like.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
The vinyl monomer containing a heterocycle includes 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine and the like.
Examples of vinylamides include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam and the like.
Examples of vinyl carboxylates include vinyl acetate, vinyl pivalate and vinyl benzoate.
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 a (meth) acrylate having an acidic group, (meth) acrylic acid), so that the solubility in an alkali developer is increased, and the alkali developability is achieved. Can be improved. However, if the ratio increases, the affinity with the solvent and the alkali-soluble resin may be lowered. Therefore, the proportion of structural units derived from a vinyl monomer having an acidic group is preferably such that the total acid value of the block copolymer becomes lower than the amine value.

When it contains the structural unit derived from the vinyl monomer which has an acidic group, 2 mass% or more is preferable in 100 mass% of A blocks, and 20 mass% or less is preferable. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate at the time of neutralization with alkali in alkali development becomes fast, and if 20% by mass or less, the hydrophilicity is high It is possible to suppress the randomness of the formed pixels.

It is preferred that the A block does not have an amino group. That is, it is preferable not to contain the vinyl monomer which has an amino group in the vinyl monomer which comprises A block. When a large amount of amino groups is present in the A block, the colorant is adsorbed to both the A block and the B block when used as a dispersant, and the dispersion performance of the colorant is degraded. 2 mass% or less is preferable, and, as for the content rate of the structural unit derived from the vinyl monomer which has an amino group in A block (The thing whose amino group is quaternized is included.), More preferably, it is 1 mass% or less. More preferably, it is 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, various structural units contained in the A block may be contained in any mode such as random copolymerization or block copolymerization in the A block. It is preferable to contain in the aspect 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 a1 block and a structural unit consisting of a2 block.

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

[Structural unit represented by general formula (1)]
The structural unit represented by the general formula (1) may be only one type or may have two or more types. By setting it as a structural unit represented by General formula (1), adsorptivity with a coloring material is high and heat resistance can be made high.

The linear hydrocarbon group represented by R ¹¹ to R ¹³ includes both linear and branched ones. Examples of the substituent that the chain hydrocarbon group represented by R ¹¹ to R ¹³ has include an alkoxy group, benzoyl group (—COC ₆ H ₅ ), and a hydroxy group. Examples of the substituent that the cyclic hydrocarbon group represented by R ¹¹ to R ¹³ has include a chain alkyl group, an alkoxy group, a hydroxy group and the like.

The group represented by R ¹¹ to R ¹³ is preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent. And methyl, ethyl, propyl and benzyl (-CH ₂ C ₆ H ₅ ) are more preferable.

Examples of the cyclic structure formed by bonding two or more of R ¹¹ to R ¹³ to each other include a 5- to 7-membered nitrogen-containing heterocyclic ring or a fused ring formed by condensing two of these. Be The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, structures represented by the following formulas (11-1), (11-2) and (11-3) can be mentioned.

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

The group represented by R ¹⁴ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. As a specific example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group etc. can be mentioned.

Examples of the alkyl group represented by R ²¹ and R ²² include a linear alkyl group, a branched alkyl group, a cyclic alkyl group and the like, preferably a linear alkyl group 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. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like can be mentioned.

Examples of the aromatic group represented by R ²¹ and R ²² include an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group and the like, and the carbon number is 6 -12 aromatic groups are preferred. Specific examples thereof include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a mesityl group and a naphthalene group.

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

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

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

The content of the structural unit represented by the general formula (1) is preferably 5% by mass or more and 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. 90 mass% or less is preferable, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less, Especially preferably, it is 70 mass% or less. By setting the content of the structural unit represented by the general formula (1) in this range, it is considered to have high affinity with the colorant.

When R ²¹ and R ²² are alkyl groups, the content of the structural unit represented by the general formula (1) is preferably 30% by mass or more, and more preferably 35% by mass in 100% by mass of the B block. The content is more preferably 40% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and 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 the general formula (1) is preferably 33% by mass or more, and more preferably 38% by mass in 100% by mass of the B block. % Or more, more preferably 43% by mass or more, preferably 85% by mass or less, more preferably 75% by mass or less, still more preferably 65% by mass or less.

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

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

The linear hydrocarbon group represented by R ³¹ or R ³² includes both linear and branched. As a substituent which the chain-like hydrocarbon group represented by said R ³¹ or R ³² has, an alkoxy group, a benzoyl group, a hydroxyl group etc. are mentioned. As a substituent which the cyclic hydrocarbon group represented by said R ³¹ or R ³² has, a chain | strand-shaped alkyl group, an alkoxy group, a hydroxy group etc. are mentioned.

Examples of the group represented by R ³¹ or R ³² include an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent. Preferably, a methyl group, an ethyl group, a propyl group and a benzyl group are more preferable.

Examples of the cyclic structure formed by combining R ³¹ or R ³² with each other include a 5- to 7-membered nitrogen-containing heterocyclic ring or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, structures represented by the following formulas (31-1), (31-2), and (31-3) can be mentioned.

[In the general formulas (31-1), (31-2), and (31-3), R ³⁵ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4; n represents 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, and more preferably an alkylene group having 1 to 5 carbon atoms. As a specific example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group etc. can be mentioned.

The content of the structural unit represented by the general formula (3) is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably 30% by mass in 100% by mass of the B block. The content is not less than 95% by mass, more preferably not more than 70% by mass, still more preferably not more than 65% by mass, and particularly preferably not more than 40% by mass. By setting the content of the structural unit represented by the general formula (3) in this range, it is considered to have high affinity with the colorant.

The B block may be only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (3), or other structural units may be included. From the viewpoint of maintaining the affinity to the colorant, the total content of the structural unit represented by the general formula (1) in the B block and the structural unit represented by the general formula (3) is 80% by mass or more Is more preferably 90% by mass or more, still more preferably 95% by mass or more. The mass ratio of the structural unit represented by the general formula (1) in the B block to the structural unit represented by the general formula (3) (Structural unit represented by the formula (1) / Table (3) 30/70 or more is preferable, More preferably, it is 35/65 or more, More preferably, it is 40/60 or more, 90/10 or less is preferable, More preferably, it is 85/15 or less, More preferably, 80/20 or less.

Moreover, it is preferable that B block does not substantially contain the structural unit derived from the vinyl monomer which has an acidic group. That is, 5 mass% or less is preferable in 100 mass% of B blocks, as for the content rate of the structural unit derived from the vinyl monomer which has an acidic group, 2 mass% or less is more preferable, and 1 mass% or less is more preferable.

Specific examples of the vinyl monomer that can form the other structural unit of the B block can be the same as those exemplified as specific examples of the vinyl monomer that can form the other structural unit of the A block.

When two or more structural units are contained in the B block, various structural units contained in the B block may be contained in any mode such as random copolymerization or block copolymerization in the B block. It is preferable to contain in the aspect 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 b1 block and a structural unit consisting of 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-B) m} type, _(a-B) m -A type, _(B-a) m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) the group consisting of It is preferable that it is a copolymer having at least one kind of structure selected from Among them, from the viewpoint of handling during processing and physical properties of the composition, an AB diblock copolymer or an ABA triblock copolymer is preferable, and heat resistance and alkali development are preferable. From the viewpoint of the properties, the AB type diblock copolymer is more preferable. In the case of an ABA type triblock copolymer, two A blocks located at both ends may be identical to or different from each other.

The content of 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 in 100% by mass of the whole block copolymer. More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less. The content of B block is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and preferably 50% by mass or less in 100% by mass of the entire block copolymer. More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less. By adjusting the contents of the A block and the B block within the above range, it is possible to achieve both heat resistance and dispersion performance when used as a dispersant in a well-balanced manner.

The mass ratio of A block to B block (A block / B block) in the block copolymer is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, 95 / 5 or less is preferable, More preferably, it is 90/10 or less, More preferably, it is 80/20 or less. If the mass ratio of the A block and the B block is within the above range, the dispersion performance and the alkali developability at the time of use as a dispersant can be compatible in a well-balanced manner.

When the said block copolymer has A1 block and A2 block as A block, mass ratio (A1 / A2) of these is preferable 0.4 or more, More preferably, it is 0.7 or more, More preferably, 0.8 It is the above, 2.3 or less is preferable, More preferably, it is 1.5 or less, More preferably, it is 1.2 or less.

The molecular weight of the block copolymer is measured by gel permeation chromatography (hereinafter referred to as "GPC"). The weight average molecular weight (Mw) of the block copolymer is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and particularly preferably 6,000 or more. 000 or less is preferable, More preferably, it is 30,000 or less, More preferably, it is 25,000 or less, Especially preferably, it is 20,000 or less. When the weight average molecular weight is in the above range, the dispersion performance when used as a dispersant becomes better.

The molecular weight distribution (PDI) of the block copolymer is preferably 2.2 or less, more preferably 2.0 or less, and still 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 range of the molecular weight distribution, and the copolymer with uniform molecular weights. When the value is 1.0, the range of the molecular weight distribution is the narrowest. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.2, those having a small molecular weight and those having a large molecular weight are included.

The amine value of the block copolymer is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and still more preferably 30 mg KOH / g or more, from the viewpoint of the adsorptivity to the colorant and the colorant dispersibility. 200 mgKOH / g or less is preferable, More preferably, it is 150 mgKOH / g or less, More preferably, it is 100 mgKOH / g or less.

When the block copolymer contains a structural unit having an acidic group, the acid value of the block copolymer is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, and still more preferably 15 mg KOH / g or more. 50 mgKOH / g or less is preferable, More preferably, it is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less. By setting the acid value in this range, it is possible to suitably function with the binder resin (alkali-soluble resin) without impairing the affinity of the block copolymer with the colorant.

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

(Method for producing block copolymer)
As a method of producing the block copolymer, a method of producing an A block first by a polymerization reaction of a vinyl monomer, and polymerizing a monomer of the B block on the A block; producing a B block first, an A block. Method for polymerizing block monomers; Method for separately preparing A block and B block and then coupling A block and B block; A block is first prepared, B table is represented by formula (3) The monomer composition containing a vinyl monomer capable of forming a structural unit to be polymerized, and quaternizing the tertiary amine structure of part of the structural unit represented by the formula (3) in the resulting polymer Method: A monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (3) is polymerized, a monomer of A block is polymerized to this polymer, and the formula in the polymer obtained ( A method of quaternizing the tertiary amine structure of a part of the structural unit represented by); separately preparing an A block and a block having the structural unit represented by the formula (3) and cupping these blocks After ringing, a method of quaternizing the tertiary amine structure of a part of the structural unit represented by the formula (3) in the obtained polymer is mentioned.

In the block copolymer of the present invention, after the block copolymer having the structural unit represented by the formula (3) is quaternized with an alkyl halide or the like, the halogen anion is converted to a sulfate ion and / or a sulfonate ion It is also obtained by exchanging. However, in such a method, halogen tends to remain as an impurity in the block copolymer obtained. Therefore, the block copolymer of the present invention is a block copolymer having a first block and a second block, and 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 The sulfuric acid compound and / or the tertiary amine structure of the structural unit represented by the formula (3) in the block copolymer obtained after synthesizing a block copolymer having a mass% or more 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 block copolymer containing no halogen can be obtained.

The polymerization method is not particularly limited, but living radical polymerization is preferable. That is, as said block copolymer, what was superposed | polymerized by living radical polymerization is preferable. In conventional radical polymerization methods, not only the initiation reaction and the growth reaction, but also the termination reaction and the chain transfer reaction cause the deactivation of the growth terminal and tend to be a mixture of polymers of various molecular weights and heterogeneous compositions. On the other hand, in the living radical polymerization method, the termination reaction and chain transfer hardly occur while maintaining the simplicity and versatility of the conventional radical polymerization method, and the growth terminal grows without being inactivated, so It is preferable at the point which manufacture of the polymer of precise control and a uniform composition is easy.

In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); an organic tellurium compound depending on the method of stabilizing the polymerization growth terminal There is a method such as a method to use (TERP method). Since the ATRP method uses an amine complex, it may not be possible to use without protecting the acid group of the vinyl monomer having an acid group. The RAFT method is less likely to have a low molecular weight distribution when various monomers are used, and may have problems such as sulfur odor and coloring. Among these methods, it is preferable to use the TERP method from the viewpoint of the variety of usable monomers, molecular weight control in the polymer 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, and, for example, WO 2004/14848, WO 2004/14962, WO No. 2004/072126 and WO 2004/096870.

Specific polymerization methods of the TERP method include the following (a) to (d).
(A) The vinyl monomer is polymerized using the organic tellurium compound represented by the general formula (4).
(B) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (4) and an azo polymerization initiator.
(C) The vinyl monomer is polymerized using a mixture of the organic tellurium compound represented by the general formula (4) and the organic ditelluride compound represented by the general formula (5).
(D) A vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (4), an azo polymerization initiator and an organic ditelluride compound represented by the general formula (5).

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

The group represented by R ⁴¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and specifically, it is as follows.
As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group And linear or branched alkyl groups such as octyl group and cyclic alkyl groups such as cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
As an aryl group, a phenyl group, a naphthyl group, etc. can be mentioned.
As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group etc. can be mentioned.

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

The group represented by R 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 amido group, an oxycarbonyl group, a cyano group, an allyl group or It is a propargyl group, specifically as follows.
As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group And linear or branched alkyl groups such as octyl group and cyclic alkyl groups such as cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
As an aryl group, a phenyl group, a naphthyl group, etc. can be mentioned. Preferably it is a phenyl group.
As a substituted aryl group, a phenyl group having a substituent, a naphthyl group having a substituent, and the like can be mentioned. Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by -COR ⁴¹¹ (R ⁴¹¹ is carbon And alkyl groups, aryl groups, alkoxy groups having 1 to 8 carbon atoms or aryloxy groups), sulfonyl groups, trifluoromethyl groups and the like. In addition, one or two of these substituents may be substituted.
As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group etc. can be mentioned.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert- group. Examples include butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
As an acyl group, an acetyl group, a propionyl group, a benzoyl group etc. can be mentioned.
Examples of the amide group include —CONR ⁴²¹ R ⁴²² (R ⁴²¹ and R ⁴²² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
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), and examples thereof include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. Groups, 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.
As an allyl group, -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 And each of which is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and the respective substituents may be linked by a cyclic structure) and the like.
As a propargyl group, -CR ⁴⁵¹ R ⁴⁵² -C≡CR ⁴⁵³ (R ⁴⁵¹ , R ⁴⁵² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁵³ is a hydrogen atom, 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 (methyl-teranylmethyl) benzene, (methyl-teranylmethyl) naphthalene, ethyl-2-methyl-2-methyl-teranyl-propionate, ethyl-2- Methyl-2-n-butyl-teranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyl-teranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methyl-teranyl-propionate or (3-trimethylsilylpropargyl Organic compounds described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870). All of tellurium compounds It 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, and dicyclopropyl ditelluride. -N-butyl ditelluride, di-s-butyl ditelluride, di-t-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis -(P-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, dipyridyl ditelluride and the like can be exemplified.

The azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in conventional radical polymerization. For example, 2,2'-azobis (isobutyronitrile) (AIBN), 2,2'-azobis (2-methylbutyronitrile) (AMBN), 2,2'-azobis (2,4-dimethylvaleronitrile) ) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid ) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4 -Dimethylvaleronitrile) (V-70), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) [Lopane], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propyl Azoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), or 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) can be exemplified.

The polymerization step is a container substituted with an inert gas, and the vinyl monomer and the organic tellurium compound of the general formula (4) are further added according to the type of vinyl monomer for the purpose of reaction promotion, control of molecular weight and molecular weight distribution, etc. An azo polymerization initiator and / or an organic ditelluride compound of the general formula (5) are mixed. At this time, nitrogen, argon, helium etc. can be mentioned as an inert gas. Preferably, argon and nitrogen are good.

The use amount of the vinyl monomer in the above (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the target copolymer. The amount of the vinyl monomer is preferably 5 mol to 10000 mol with respect to 1 mol of the organic tellurium compound of the general formula (4).

When using together the organic tellurium compound of General formula (4) of said (b), and an azo polymerization initiator, 0.01 mol-10 mol of azo polymerization initiators are carried out with respect to 1 mol of organic tellurium compounds of General formula (4) It is preferable to

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

When the organic tellurium compound of the general formula (4) of (d), the organic ditelluride compound of the general formula (5) and the azo polymerization initiator are used in combination, 1 mol of the organic tellurium compound of the general formula (4) The organic ditelluride compound of the formula (5) is preferably 0.01 mol to 100 mol, and the azo polymerization initiator is preferably 0.01 mol to 10 mol based on 1 mol of the organic tellurium compound of the general formula (4).

The polymerization reaction may be carried out without a solvent, but may be carried out by stirring the mixture using an aprotic solvent or a protic solvent generally used in radical polymerization. Aprotic solvents which 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 And carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene and the like. In addition, examples of the protic solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol and the like.

The amount of the solvent used may be appropriately adjusted, for example, 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 vinyl monomer. Preferably, it is 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 reaction 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 performed at normal pressure, but may be increased or decreased.

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

The growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR ⁴¹ (wherein R ⁴¹ is the same as the above) derived from the tellurium compound, and is deactivated by the operation in air after the polymerization reaction is completed. However, tellurium atoms may remain. It is preferable to remove the tellurium atom because the copolymer in which the tellurium atom remains at the end is colored or has poor thermal stability.

As a method of removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbents, etc .; ion exchange resin etc. Method of adsorbing metal; Oxidative decomposition of tellurium terminal of copolymer end by adding peroxide such as hydrogen peroxide solution or benzoyl peroxide or blowing air or oxygen into the system, washing with water A liquid-liquid extraction method or solid-liquid extraction method for removing residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration, which extracts and removes only those having a specific molecular weight or less; Also, these methods can be used in combination.

When the tertiary amine group of the structural unit represented by the formula (3) is quaternized, as the quaternizing agent, a sulfuric acid compound represented by the formula (6-1), a table represented by the formula (6-2) And sulfonic acid compounds.

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

Examples of the alkyl group represented by R ²¹ to R ²⁴ include a linear alkyl group, a branched alkyl group, a cyclic alkyl group and the like, preferably a linear alkyl group having 1 to 20 carbon atoms, and 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. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like can be mentioned. In Formula (6-1), R ²¹ and R ²³ are preferably the same substituent.

Examples of the aromatic group represented by R ²¹ to R ²⁴ include an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group, an aralkyloxy group and the like, and the carbon number is 6 An aromatic ring group of -12 is preferred. Specific examples thereof include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a mesityl group and a naphthalene group.

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

Examples of the sulfonic acid compounds include methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, isopropyl methanesulfonate, ethyl benzenesulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, p -Ethyl toluene sulfonate etc. are mentioned. Among these, aromatic sulfonic acids having an aromatic ring are preferable, and methyl p-toluenesulfonate and ethyl p-toluenesulfonate are particularly preferable.

As a method of quaternizing a part of the tertiary amine structure of the structural unit represented by the formula (3) in the polymer, a method of contacting the polymer with a quaternizing agent may be mentioned. Specifically, after polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (3), a method of adding a quaternizing agent to the reaction liquid and stirring it 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. The solvent to be added for dilution includes a solvent that can be used for the polymerization reaction, a protic solvent, and a mixed solvent of a solvent that can be used for the polymerization reaction and the protic solvent, and the solubility of the target block copolymer It may be selected as appropriate.

<Dispersing agent>
The dispersant according to the present invention contains the block copolymer as a main component (50% by mass or more), preferably contains 75% by mass or more of the block copolymer, and more preferably the above-mentioned block copolymer It consists only of a block copolymer. In the block copolymer, for example, the tertiary amino group in the structure (B block) or the quaternary ammonium base is strongly bonded to the acidic group of the colorant treated with the acidic colorant or the acidic group-containing dye derivative. By adsorbing this B block to the colorant, it is considered that the effect of enhancing the colorant dispersibility is exhibited. That is, since the dispersing agent of the present invention is a component that causes the colorant to be well dispersed by this action, the type of colorant to be dispersed is not particularly limited. The coloring composition using the dispersant of the present invention can be suitably used as a dispersant for color filter since it has alkali developability.

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

(Colorant)
The type of the colorant may be appropriately selected depending on the application, and examples include pigments and dyes. It is preferable that the said coloring composition contains a pigment as a coloring material from a light resistance and a heat resistant viewpoint. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable. As a pigment, the pigment of each color, such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, a purple pigment, is mentioned, for example. The structure of the pigment is azo based pigments such as monoazo based pigments, diazo based pigments, condensed diazo based pigments, diketopyrrolopyrrole based pigments, phthalocyanine based pigments, isoindolinone based pigments, isoindoline based pigments, quinacridone based pigments, indigo based pigments And pigments such as system pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and polycyclic pigments such as perinone pigments. The coloring material contained in the coloring composition may be only one kind, or may be plural kinds for adjustment of chromaticity and the like.

Specific examples of the pigment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213; I. Pigment Orange 36, 38, 43, etc .; I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, etc. blue pigments; C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, etc .; I. Pigment Violet 23, 29, 32, 50, and the like. Among these, pigments are C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 is preferred.

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

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

The colorant may contain a dye derivative as a dispersion aid. The dye derivative preferably contains an acidic dye derivative having an acidic group in order to cause it to be ionically bonded to a tertiary amino group and a quaternary ammonium base in the block copolymer contained in the dispersant and to cause adsorption. . This dye derivative is one in which an acidic functional group is introduced into the dye skeleton. As a pigment | dye frame | skeleton, the frame | skeleton same as or similar to the coloring material which comprises the coloring composition, and frame | skeleton identical or similar to the compound used as the raw material of this 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, a perylene dye skeleton and the like. As an acidic group introduce | transduced into pigment | dye frame | skeleton, a carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable. Sulfonic acid groups are preferred for the convenience of synthesis and for the degree of acidity. The acidic group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, an ether, a sulfonamide or a urethane bond. The use amount of the dye derivative is not particularly limited, but for example, 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 is usually 80% by mass, preferably 70% by mass, and preferably 60% by mass, in the total solid content of the coloring composition, from the viewpoint of brightness. Is more preferred. The lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass, in the total solid content of the coloring composition. preferable. Here, the solid content is a component other than the dispersion medium described later.

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

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

As glycol monoalkyl ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene Glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl- 3-Metoki Butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and the like. Examples of glycol dialkyl ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and the like. As glycol alkyl ether acetates, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol mono Chill ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and the like. Examples of glycol diacetates include ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate and the like. Examples of alkyl acetates include cyclohexanol acetate and the like. Examples of the ethers include amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether and the like. As ketones, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy Methyl pentanone and the like can be mentioned. As monohydric or polyhydric alcohol, 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 can be mentioned. Examples of aliphatic hydrocarbons include n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane and the like. Cycloaliphatic hydrocarbons include cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene and cumene. As chain or cyclic esters, amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate Isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone and the like can be mentioned. Examples of alkoxycarboxylic acids include 3-methoxypropionic acid, 3-ethoxypropionic acid and the like. Examples of halogenated hydrocarbons include butyl chloride and amyl chloride. Examples of ether ketones include methoxymethyl pentanone and the like. Examples of nitriles include acetonitrile and benzonitrile. The organic solvent is a glycol alkyl ether acetate, a glycol monoalkyl ether, or a monohydric or polyhydric alcohol from the viewpoint of the dispersibility of a coloring material, the solubility of a dispersant, the coatability of a coloring composition, etc. Is preferred. The solvent contained in the coloring composition may be only one type or a plurality of types.

When forming the pixels of the color filter by photolithography, the boiling point of the dispersion medium is preferably 100 ° C. to 200 ° C. (pressure 1013.25 hPa conditions, hereinafter the same applies to all the boiling points), and 120 ° C. to 170 ° C. More preferable. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferable in terms of good balance of coating properties, surface tension and the like and relatively high solubility of the component in the coloring composition. The 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 more in combination. By using such a dispersion medium having a high boiling point in combination, the colored composition becomes difficult to dry, and the destruction of the mutual relationship of the colored composition due to rapid drying can be suppressed. The content of the dispersion medium having a boiling point of 150 ° C. or more is preferably 3% by mass to 50% by mass with respect to 100% by mass of the entire dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress that a coloring material or the like precipitates and solidifies at the tip of the slit nozzle to generate a foreign matter defect. If the content is 50% by mass or less, the drying speed of the coloring composition becomes slow, and the occurrence of problems such as prolongation of the drying time and pin marks of prebaking can be suppressed in color filter production described later. The dispersion medium having a boiling point of 150 ° C. or more may be a glycol alkyl ether acetate, and in this case, a dispersion medium having a boiling point of 150 ° C. or more may not be separately contained.

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

In the color filter production by the ink jet method, since the ink emitted from the nozzles is very fine such as several pL to several tens pL, the dispersion medium evaporates before the ink lands around the nozzle opening or in the pixel bank. Tend to concentrate and dry. In order to avoid this, the boiling point of the dispersion medium is preferably high, and specifically, it is preferable to include a dispersion medium having a boiling point of 180 ° C. or more. More preferably, it contains a dispersion medium having a boiling point of 200 ° C. or more, particularly preferably 220 ° C. or more. The high boiling point solvent having a boiling point of 180 ° C. or more is preferably 50% by mass or more, more preferably 70% by mass or more, with respect to 100% by mass of the entire dispersion medium contained in the colored resin composition. % Or more is most preferable. By setting the content to the above lower limit value or more, there is a tendency that the effect of preventing evaporation of the solvent from droplets can be sufficiently exhibited.

The content of the dispersion medium in the coloring composition is not particularly limited, and can be appropriately adjusted. The upper limit value of the content of the dispersion medium in the coloring composition is usually 99% by mass. The lower limit value of the content of the dispersion medium in the coloring composition is usually 70% by mass and preferably 75% by mass in consideration of the viscosity suitable for application of the coloring composition. The dispersion 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 (except for the above-mentioned block copolymer). Thereby, the alkali developability of the coloring composition and the binding property to the substrate can be enhanced. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group. As the binder resin, for example, with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, an unsaturated monobasic acid in at least a part of the epoxy group that the copolymer has Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxy group generated by the addition reaction; a linear alkali-soluble resin having a carboxy group in the main chain; A resin in which an epoxy group-containing unsaturated compound is added to a carboxy group part of a carboxy group-containing resin; (meth) acrylic resin; epoxy (meth) acrylate resin having a carboxy group; Alternatively, two or more kinds can be mixed and used.

As a preferred embodiment of the binder resin, a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer, a structural unit derived from (meth) acrylate and styrene, a structural unit derived from a carboxy group-containing vinyl monomer And random copolymers containing a structural unit derived from (meth) acrylate and (meth) acrylate. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. As said (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 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 ( Meta) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. That.

The total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from (meth) acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably It is 70 mass% or more. 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, and still more preferably 20% by mass or more, and 90% by mass or less. Is preferable, and more preferably 70% by mass or less.

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

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

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

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

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

The binder resin contained in the coloring composition may be only one type or a plurality of types. In the coloring composition, the content of the binder resin is preferably 5 parts by mass to 200 parts by mass, and more preferably 10 parts by mass to 100 parts by mass, with respect to 100 parts by mass of the colorant. More preferably, it is part to 80 parts by mass.

(Crosslinking agent)
The coloring composition may contain a crosslinking agent. The crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. The crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups. The said crosslinking agent can be used individually or in mixture of 2 or more types.

Specific examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxy group with polyfunctional isocyanate, (meth) acrylate having hydroxy group The polyfunctional (meth) acrylate etc. which have a carboxy group obtained by making and an acid anhydride react can be mentioned.

Examples of the aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; and trivalent or more such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Aliphatic polyhydroxy compounds of the formula: Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Pentaerythritol hexa (meth) acrylate, glycerol dimethacrylate and the like can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydrides include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, etc .; pyromellitic anhydride, biphenyl tetracarboxylic acid And tetrabasic acid dianhydrides such as acid dianhydride and benzophenone tetracarboxylic acid dianhydride.

In the coloring composition of the present invention, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant. If the content of the crosslinking agent is too low, sufficient curability may not be obtained. On the other hand, when the amount of the crosslinking agent is too large, the alkali developability of the coloring composition of the present invention is lowered, and there is a tendency that background stains, film residue and the like tend to occur on the unexposed area substrate or light shielding layer. .

(Photopolymerization initiator)
The coloring composition preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The said photoinitiator is a compound which generate | occur | produces the active species which can start superposition | polymerization of a crosslinking agent by exposure of radiations, such as a visible ray, an ultraviolet-ray, a far infrared ray, an electron beam, X ray.

Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, and α-diketones. There can be mentioned, for example, based 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 parts by mass to 120 parts by mass, and particularly preferably 1 parts by mass to 100 parts by mass with respect to 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, while if it is too large, the formed colored layer tends to fall off the substrate during development. .

(Other additives)
In the coloring composition, other additives can be blended in addition to the additives as long as the preferred physical properties of the present invention are not impaired. Other additives include dispersants other than the block copolymer, sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, Plasticizers, organic carboxylic acid compounds, organic carboxylic acid anhydrides, pH adjusters, antioxidants, UV absorbers, light stabilizers, preservatives, fungicides, anticoagulants, adhesion improvers, development improvers, A storage stabilizer etc. can be mentioned.

As the dispersant excluding the block copolymer, a urethane based dispersant, a polyethyleneimine based dispersant, a polyoxyethylene alkyl ether based dispersant, a polyoxyethylene glycol diester based dispersant, a sorbitan aliphatic ester based dispersant, a fat Group modified polyester type dispersing agent etc. are mentioned.

As the sensitizing dye, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 2,4-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) benzothiazo , 2- (p-Dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) And the like)) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine and the like.

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

As the nonionic surfactant, fluorine-based surfactants (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra) Fluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane etc.), Corn-based surfactants, polyoxyethylene-based surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid Esters, glycerine fatty acid esters, polyoxyethylene glycerine fatty acid esters, pentaerythrite fatty acid esters, polyoxyethylene pentaerystic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters And polyoxyethylene sorbite fatty acid esters and the like).

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

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

Examples of 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 , A carboxyl group is directly bonded to a phenyl group such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarballylic acid, aconitic acid, benzoic acid and phthalic acid Examples thereof include carboxylic acids, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond.

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

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

The colored composition can be suitably used for a color filter because it has alkali developability.

The color filter of the present invention is provided with a colored layer formed using the above-mentioned coloring composition. As a method of manufacturing a color filter, the following method is mentioned, for example. First, thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins and polymethyl methacrylate resins, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, various glasses For example, after applying a coloring composition of the present invention in which a red pigment is dispersed, on a transparent substrate such as, for example, prebaking is performed to evaporate a solvent (dispersion medium) to form a coating film. Next, the coating film is exposed to light through a photomask and then developed using an alkaline developer (an organic solvent or an aqueous solution containing a surfactant and an alkaline compound, etc.) to dissolve and remove the unexposed area of the coating film. Do. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement. Then, using each green or blue coloring composition and applying, prebaking, exposing, developing and postbaking each coloring composition in the same manner as above, the green pixel array and the blue pixel array are the same substrate Form sequentially on top. As a result, a color filter in which pixel arrays of three primary colors of red, green and blue are disposed on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above. In addition, a black matrix may be provided on a transparent substrate used to form a red, green and blue three primary color pixel array.

When the coloring composition is applied to the substrate, an appropriate application 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 can be employed. In particular, spin coating or slit die coating is preferably employed.
A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film (ITO or the like) is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter.

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

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these specific examples. Moreover, the various physical-property measurement measured with the following apparatuses. The meanings of the abbreviations are as follows.
MMA: methyl methacrylate BMA: n-butyl methacrylate EHMA: 2-ethylhexyl methacrylate M9EGM: methoxypolyethylene glycol monomethacrylate (addition mole number 9 of ethylene oxide) (trade name: Blenmer (registered trademark) PME-400, manufactured by NOF Corporation)
M4EGM: Methoxy polyethylene glycol monomethacrylate (addition mole number 4 of ethylene oxide) (trade name: Blenmer (registered trademark) PME-200, manufactured by NOF Corporation)
PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Co., Ltd., Plaxel® FM5)
MAA: methacrylic acid DMAEMA: 2- (dimethylamino) ethyl methacrylate DMAPMAm: N- (3-dimethylaminopropyl) methacrylamide BTEE: ethyl-2-methyl-2-n-butyl-teranyl-propionate DBDT: dibutyl ditelluride AIBN : 2,2'-azobis (isobutyronitrile)
ADVN: Azobis (2,4-dimethyl valeronitrile)
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) measurement apparatus (manufactured by Bruker, model: AVANCE 500 (frequency 500 MHz)). With respect to the obtained NMR spectrum, the integral ratio 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 Corporation, model: HLC-8320). Column: One SHODEX KF-603 (Φ 6.0 mm × 150 mm) (manufactured by SHODEX), mobile phase: 30 mmol / L lithium bromide-30 mmol / L acetic acid-N-methylpyrrolidone solution, detector: differential refractometer used. As the measurement conditions, the column temperature was 40 ° C., the sample concentration was 10 mg / mL, the sample injection amount was 10 μL, and the flow rate was 0.2 mL / min. Prepare a calibration curve (calibration curve) using polystyrene (molecular weight 70, 500, 37, 900, 19, 920, 10, 200, 4, 290, 2, 630, 1, 150) as a standard substance, and weight average Molecular weight (Mw) and number average molecular weight (Mn) were measured. The molecular weight distribution (PDI = Mw / Mn) was calculated from these measured values.

(Amine value)
The amine value is represented by the mass of potassium hydroxide (KOH) equivalent to the basic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-06, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated by the following equation, with the inflection point of the titration pH curve as the titration end point.
B = 56. 11 x Vs x 0.1 x f / w
B: Amine value (mg KOH / g)
Vs: Use 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 of measurement sample (g) (solid content conversion)

(Acid number)
An acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, several drops of a phenolphthalein ethanol solution were added as an indicator, and neutralization titration was performed with a 0.1 mol / L potassium hydroxide / ethanol solution. The acid value (A) was calculated by the following equation.
A = 56. 11 x Vs x 0.1 x f / w
A: Acid value (mg KOH / g)
Vs: Use amount (mL) of 0.1 mol / L potassium hydroxide / ethanol solution required for titration
f: titer of 0.1 mol / L potassium hydroxide / ethanol solution w: mass of measurement sample (g) (solid content conversion)

(Content of halogen anion)
The sample preparation was performed as follows. About 100 mg of the reaction liquid after the quaternization step was introduced into a combustion furnace (trade name: AQF-2100H, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The heater of the combustion furnace was 900 ° C. (inner side), the gas flow rate was 200 mL / min of argon, 400 mL / min of oxygen, 100 mL / min of argon for humidification, and the combustion furnace residence time was 15 minutes. The exhaust gas was captured by a collector (trade name: AU-250, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Using ultrapure water as the absorbing solution, 35 mL of the resulting water-absorbing solution was diluted to 50 mL with ultrapure water to prepare a sample solution.
The content of the halogen anion was measured using ion chromatography (trade name: DIONEX ICS-1600, manufactured by Thermo Scientific). The column used was Ion Pac AS-12A (manufactured by DIONEX), and the eluent was an eluent for anion analysis (trade name: manufactured by AS12A, manufactured by DIONEX). The measurement conditions were such that the sample injection amount was 25 μL and the flow rate was 1.5 mL / min. A calibration curve (calibration curve) was prepared using a standard solution having a chloride anion concentration of 0, 5 ppm, 1 ppm, and 2 ppm as a standard substance to calculate a chloride anion concentration.

(Heating weight loss temperature)
It measured using the thermogravimetry * differential-heat simultaneous measuring apparatus (TG-DTA) (The HITACHI make, TG / DTA6300). The measurement sample was vacuum dried at a temperature of 130 ° C. for 1 hour before the measurement. The measurement conditions were a sample weight of about 10 mg, an air inflow of 200 ml / min, a temperature rise rate of 10 ° C./min, and a measurement temperature range of 40 ° C. to 600 ° C. The temperature at which the sample mass decreased by 10% was read from the obtained TG curve, and this was taken as the heating weight loss temperature.

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

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

<Production of prequaternized copolymer>
(No. 1)
A flask equipped with an argon gas inlet tube and a stirrer was placed in a flask equipped with MMA (99.9 g), BMA (64.8 g), EHMA (59.5 g), M9 EGM (21.6 g), AIBN (0.74 g), PMA (163) 8 g) were charged and after replacing 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 argon-substituted was added to the reaction solution, and reacted at 60 ° C. for 20 hours to polymerize the second block. The conversion of DMAEMA was 99%. Further, the monomer for the first block remaining in the reaction solution was also polymerized and taken into the second block. The polymerization rate of the first block monomer remaining in these reaction solutions was 100%. In addition, the content rate of each structural unit in a copolymer was computed from the preparation ratio and the polymerization rate of the monomer used for the polymerization reaction.

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

(No. 2-5)
Before quaternization copolymer No. In the same manner as in the production method of No. 1, the copolymer before quaternization No. 1 is prepared. Two to five were made. Table 1 shows raw material monomers used, organic tellurium compounds, organic ditellurilide compounds, azo polymerization initiators, solvents, reaction conditions, and polymerization rates. In addition, the content rate of each structural unit in a copolymer was computed from the preparation ratio and the polymerization rate of the monomer used for the polymerization reaction.

(No. 6)
In a flask equipped with an argon gas inlet tube and a stirrer, MMA (4.23 g), BMA (2.74 g), EHMA (2.52 g), M9 EGM (0.91 g), DMAPM Am (3.71 g), n- Dodecanethiol (0.28 g) and PMA (21.0 g) were charged, and after argon substitution, the temperature was raised to 78 ° C. MMA (8.45 g), BMA (5.48 g), EHMA (5.03 g), M9EGM (1.83 g), DMAPM Am (7.43 g), ADVN (0) while keeping the solution at 78 ° C. .85 g), n-dodecanethiol (0.56 g) and PMA (42.3 g) were added dropwise over 1.5 hours. After 60 minutes from the end of the dropwise addition, ADVN (0.11 g) and PMA (2.0 g) were added and reacted for 1 hour while maintaining the temperature at 78 ° C. Further, ADVN (0.11 g) and PMA (2.0 g) were added and reacted for 1 hour. Furthermore, ADVN (0.11 g) and PMA (2.0 g) were added and allowed to react for 1 hour. Furthermore, ADVN (0.11 g) and PMA (2.0 g) were added and allowed to react for 2 hours. The resulting reaction solution was cooled to room temperature, and the prequaternized copolymer No. 1 A PMA solution of 6 was obtained. The non-volatile content was 34.9%.

(No. 7)
Pre-quaternized copolymer No. 1 was prepared except that DMAMAPMAm was changed to DMAEMA. In the same manner as in the production method of No. 6, the copolymer before quaternization No. I got seven. The non-volatile content was 35.4%.

<Quaternization process of copolymer>
The quaternization precopolymer was dissolved in PMA or PMA / MP mixed solvent (PMA: MP = 1: 1 (mass ratio)) to prepare PMA solution or PMA / MP solution. The PMA solution or PMA / MP solution of the resulting quaternized precopolymer was placed in an eggplant flask. To this solution, dimethyl sulfate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), methyl p-toluenesulfonate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) or benzyl chloride was added dropwise while stirring at room temperature. Thereafter, the mixture was reacted at 60 ° C. with stirring. This was cooled to obtain a solution of a quaternized block copolymer. Tables 3 and 4 show the quaternizing agent used in the quaternization step, the solvent, and the reaction conditions. 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 which does not have the structural unit of the general formula (1) and a B block which has the structural unit of the general formula (1). Copolymer No. 8 to 12 are cases where the counter anion of the B block is a chloride ion. For each of these copolymers, when the composition of the quaternized prepolymer is the same, the counter ion of the B block is represented by the formula ((copolymer No. 8 to 12) compared with the counter ion The heating weight reduction temperature is higher and the heat resistance is better in the case of the copolymer represented by 2-1) or the formula (2-2) (copolymers Nos. 1 to 7).

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

<Production of Colored Composition>
(Manufacturing of binder resin)
In a flask equipped with an argon gas inlet tube and a stirrer, MAA (20.0 g), BzMA (80.0 g) and PMA (290.0 g) are charged, and 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 keeping the solution at 90 ° C., MAA (40.0 g), BzMA (160.0 g), AIBN (3.0 g), n-dodecanethiol (4.0 g), PMA (25.0 g) were added to the solution. It dripped over 1.5 hours. 60 minutes after completion of dropping, the temperature is raised to 110 ° C., AIBN (0.3 g) and PMA (5.0 g) are added and reacted for 1 hour, and further AIBN (0.3 g) and PMA (PM) 5.0 g) was added and allowed to react for 1 hour, and further AIBN (0.3 g) and PMA (5.0 g) were added and allowed to react for 1 hour.

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

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

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

Coloring composition No. The coloring composition for color filters using 1 to 7 was prepared using the copolymer No. 1 as a dispersant. 1 to 7 are contained. These color filter coloring compositions had a low viscosity even after one week, and were also excellent in alkali developability. In particular, as a dispersant, copolymer No. 1 in which the A block has an acidic group. Although the coloring composition for color filters using 2 and 3 had the low quaternization rate, alkali developability was further excellent.

Coloring composition No. The coloring composition for color filters using 8 to 12 was prepared from the copolymer No. 1 as a dispersant. Contains 8-12. These color filter coloring compositions have low viscosity even after one week. In addition, these coloring compositions for color filters are copolymer No. 1 It is considered that the heat resistance of the resulting color filter is low because the heat resistance of 8 to 12 is low.

Coloring composition No. The coloring composition for color filters using 13 and 14 was prepared from copolymer No. 1 as a dispersant. Contains 13 or 14 These colored composition for color filters gelled one week after preparation. Therefore, copolymer no. 13 and 14 have poor dispersion stability.

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

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

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

(Embodiment 4)
The block copolymer according to any one of embodiments 2 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 has a linear alkyl group-containing (meth) acrylate, a cyclic alkyl group-containing (meth) acrylate, an aromatic group-containing (meth) acrylate, and a polyalkylene glycol structural unit (meth ) Acrylate, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone modified hydroxy group, (meth) acrylate having an alkoxy group, (meth) acrylate having an oxygen-containing heterocyclic group, having an acidic group (meth The block copolymer according to any one of the embodiments 1 to 4, which is at least one monomer selected from the group consisting of acrylates and (meth) acrylic acid.

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

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

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

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

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

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

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

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

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

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

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

Embodiment 20
20. A colored composition comprising the dispersant according to claim 18 or 19, a colorant, a dispersion medium and a binder resin.

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

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

Claims

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

[In formula (1), R 11 , R 12 and R 13 each independently represent a linear or cyclic hydrocarbon group which may have a substituent. Two or more of R 11 , R 12 and R 13 may be bonded to each other to form a cyclic structure. R 14 represents a chain-like divalent hydrocarbon group. R 15 represents a hydrogen atom or a methyl group. Z − represents a counter ion represented by the general formula (2-1) or the 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 according to claim 1, wherein the B block further contains a structural unit represented by the following general formula (3).

[In formula (3), R 31 and R 32 each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R 31 and R 32 may be bonded to each other to form a cyclic structure. R 33 represents a linear divalent hydrocarbon group. R 34 represents a hydrogen atom or a methyl group. ]
3. The block copolymer according to claim 1, wherein a content of the structural unit represented by the formula (1) is 5% by mass to 90% by mass in 100% by mass of the B block.
The block copolymer according to any one of claims 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. .
The (meth) acrylic vinyl monomer has a linear alkyl group-containing (meth) acrylate, a cyclic alkyl group-containing (meth) acrylate, an aromatic group-containing (meth) acrylate, and a polyalkylene glycol structural unit (meth ) Acrylate, (meth) acrylate having a hydroxy group, (meth) acrylate having a lactone modified hydroxy group, (meth) acrylate having an alkoxy group, (meth) acrylate having an oxygen-containing heterocyclic group, having an acidic group (meth The block copolymer according to any one of claims 1 to 4, which is at least one monomer selected from the group consisting of acrylate and (meth) acrylic acid.
The block copolymer according to any one of claims 1 to 5, wherein the content of the structural unit derived from the (meth) acrylic vinyl monomer is 80% by mass or more in 100% by mass of the A block.
The block copolymer according to any one of claims 1 to 6, wherein a mass ratio of A block to B block (A block / B block) in the block copolymer is 50/50 to 95/5. .
The block copolymer according to any one of claims 1 to 7, wherein the amine value of the block copolymer is 10 mg KOH / g to 200 mg KOH / g.
The block copolymer according to any one of claims 1 to 8, which is an AB type diblock copolymer or an ABA type triblock copolymer.
The block copolymer according to any one of claims 1 to 9, wherein a molecular weight distribution (PDI) of the block copolymer is 2.2 or less.
The block copolymer according to any one of claims 1 to 10, wherein a weight average molecular weight (Mw) of the block copolymer is 3,000 to 40,000.
The block copolymer according to any one of claims 1 to 11, wherein the block copolymer is polymerized by living radical polymerization.
A dispersant comprising the block copolymer according to any one of claims 1 to 12.
The dispersant according to claim 13, which is for color filters.
A coloring composition comprising the dispersant according to claim 13 or 14, a colorant, a dispersion medium, and a binder resin.
A color filter comprising a colored layer formed using the coloring composition according to claim 15.