KR102032076B1 - Block Copolymers, Dispersants, and Pigment Dispersion Compositions - Google Patents

Abstract

[Problem] A block copolymer which can be used as a dispersant and has excellent heat resistance is provided.
[Solution] The block copolymer includes an A block containing a structural unit derived from a vinyl monomer having an acid group, a structural unit represented by the following general formula (1), and a structural unit represented by the following general formula (2). It is characterized by having a B block to include.

[In formula (1), (2), R <^11> , R <^12> , R <^13> , R <^21> and R <^22> respectively independently represents the 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 ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ¹ and X ² represent a divalent linking group. R <^14> and R <^23> represents a hydrogen atom or a methyl group. Y ⁻ represents at least one member selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions.]

Description

Block Copolymers, Dispersants, and Pigment Dispersion Compositions

The present invention relates to block copolymers, dispersants and pigment dispersion compositions.

Background Art Conventionally, in the production of color filters used for liquid crystal displays and the like, pigment dispersing methods, dyeing methods, electrodeposition methods, printing methods, and the like are known as methods for providing color materials to substrates. Among these, the pigment dispersion method is widely used from the viewpoint of spectral characteristics, durability, pattern shape, and precision. In the pigment dispersion method, the coating film which consists of a pigment dispersion composition which mixed the pigment, a dispersing agent, and a dispersion medium (solvent), for example is formed on a board | substrate, and it exposes through a photomask of a desired pattern shape, and alkali develops.

Moreover, in manufacture of a liquid crystal display, after forming the pattern shape of a color material, the transparent electrode for driving a liquid crystal is formed by vapor deposition or sputtering on it, and the alignment film for orientating a liquid crystal in a fixed direction is formed on it. . In order to fully acquire the performance of these transparent electrodes and an oriented film, these formation is generally performed at high temperature 200 degreeC or more. However, when many resin type dispersants are used for the said pigment dispersion composition, heat resistance, such as a fall of contrast ratio of a color filter, a color change, before and after the process with high heat becomes a problem.

Then, the resin type dispersing agent which improved heat resistance is proposed. For example, in Patent Document 1, in order to obtain a color filter having excellent heat resistance, an AB block copolymer composed of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base is used as a pigment dispersant for color filters. Is disclosed (see Patent Document 1 (claim 1, paragraph 0049 to 0058)).

In addition, Patent Literature 2 uses an AB block copolymer composed of an A block having an acid group in a side chain and a B block having an amino group or a quaternary ammonium salt group in the side chain, as a pigment dispersant, thereby applying characteristics and long-term storage stability and alkali developability. This improvement is disclosed (refer patent document 2 (claim 1, paragraph 0031-0034, 0038-0040)).

Japanese Patent Laid-Open No. 2012-068559 Japanese Patent Publication No. 2013-203887

Conventionally, although the resin type dispersing agent which improved heat resistance was proposed, there existed a problem that the heat resistance of a resin type dispersing agent was not enough. This invention is made | formed in view of the said situation, For example, it aims at providing the block copolymer which can be used as a dispersing agent and has the outstanding heat resistance.

The block copolymer of this invention which can solve the said subject is represented by the A block containing the structural unit derived from the vinyl monomer which has an acidic group, the structural unit represented by General formula (1), and general formula (2) It is characterized by having a B block including a structural unit.

[In Formula (1), R <^11> , R <^12> and R <^13> respectively independently represents the 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. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents at least one member selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions.]

[In formula (2), R <^21> and R <^22> represents the linear or cyclic hydrocarbon group which may respectively have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

In the polymer having a conventional quaternary ammonium base, a halogen anion is generally used as a counter ion of the quaternary ammonium cation. Such a polymer containing a halogen anion is considered to be inferior in heat resistance because it causes a detachment reaction of counter ions in a high temperature atmosphere. The block copolymer of the present invention is excellent in heat resistance because the counter ions of the quaternary ammonium cations in the class B block are aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions or aromatic carboxylic acid anions. Moreover, since the block copolymer of this invention has A block which has an acidic group, and B block which has a specific structure, it can be used as a dispersing agent.

It is preferable that the said block copolymer is an A-B type block copolymer. In the said block copolymer, it is preferable that the content rate of the structural unit derived from the vinyl monomer which has the said acidic group is 2 mass%-20 mass% in 100 mass% of said A blocks. In the said block copolymer, it is preferable that the content rate of the structural unit represented by the said General formula (1) is 30 mass%-85 mass% in 100 mass% of said B blocks. It is preferable that content of the said A block is 35 mass%-85 mass% in 100 mass% of block copolymers.

This invention also includes the 1st composition containing the said block copolymer, and the 2nd composition obtained by washing and drying the said 1st composition. It is preferable that the molecular weight distribution (PDI) of the block copolymer contained in a said 1st composition is 2.0 or less. Moreover, the dispersing agent containing the said block copolymer, a 1st composition, or a 2nd composition is contained in this invention. In addition, the present invention also includes a pigment dispersion composition containing the dispersant, the pigment, and the dispersion medium. As such a composition, the pigment dispersion composition for color filters is mentioned.

The manufacturing method of the block copolymer of this invention is a block containing the structural unit derived from the vinyl monomer which has an acidic group, the structural unit represented by following formula (2), and the structural unit represented by following formula (3). In the process (A) of preparing the precursor of the block copolymer which has the B block containing, and the precursor of the block copolymer obtained by the said process (A), it is aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid. It is characterized by including the process (B) which acts at least 1 sort (s) of alkali metal salt chosen from the group which consists of, and obtains a block copolymer.

[In formula (2), R <^21> and R <^22> represents the linear or cyclic hydrocarbon group which may respectively have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

[In Formula (3), R <^31> , R <^32> and R <^33> respectively independently represents the linear or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ^- represents a halogen anion.]

By using the alkali metal salt of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, or aromatic carboxylic acid in the said process (B). It becomes easy to exchange (anion exchange) from the counter ionol halogen anion of the quaternary ammonium cation to an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion or an aromatic carboxylic acid anion.

Regarding the anion exchange in this step (B), each ion is classified based on the HASB law. For example, halide ions (eg, chloride ions) are classified as solid bases because of their high electronegativity and low polarization rate. Alkali metal ions (eg potassium ions) are classified as hard acids. Aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions having a? Electron system of an aromatic ring are considered to be classified as soft bases. Quaternary ammonium ions in the polymer are thought to be classified as soft acids. According to the law of HSAB, a combination of acids and bases of the same hardness, such as soft bases for soft acids and hard bases for hard acids, is strong. It is thought that anion exchange becomes easy by generating the ion pair which has strong binding force in the said anion exchange.

In the said manufacturing method, in the said process (A), it is preferable to prepare the precursor of the said block copolymer using living radical polymerization. Moreover, it is preferable that the said manufacturing method is equipped with the process (C) of washing the block copolymer obtained at the said process (B).

According to this invention, it can use as a dispersing agent, for example, and can provide the block copolymer which has the outstanding heat resistance.

Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an illustration. This invention is not limited to the following embodiment at all.

<1 block copolymer>

The block copolymer of this invention is an A block containing the structural unit derived from the vinyl monomer which has an acidic group, and the structural unit represented by the structural unit represented by General formula (1) mentioned later, and General formula (2) mentioned later Characterized in that having a B block comprising a.

In the present invention, "A block" may be referred to as "A segment", and "B block" may be referred to as "B segment". In the present invention, the "vinyl monomer" refers to a monomer having a carbon-carbon double bond capable of radical polymerization in a molecule. The "structural unit derived from a vinyl monomer" means the structural unit which the carbon-carbon double bond which can be radically polymerized of a vinyl monomer superposed | polymerized and became a carbon-carbon single bond. "(Meth) acryl" means "at least one of an acryl and methacryl". "(Meth) acrylate" means "at least one of an acrylate and a methacrylate." "(Meth) acryloyl" means "at least one of acryloyl and methacryloyl".

Various structural components, etc. of the block copolymer of this invention are demonstrated below.

(1.1 A block)

A block is a polymer block which has a structural unit derived from the vinyl monomer which has an acidic group. An A block is considered to have an acidic group, and alkali image development becomes easy. Therefore, the said block copolymer can be used suitably for the pigment dispersion composition for color filters used for manufacture of the color filter which employ | adopted alkali image development.

Examples of the acidic group include a carboxyl group (-COOH), a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ), a phosphonic acid group (-PO ₃ H ₂ ), and a phosphinic acid group (-PO ₂ H ₂ ) Can be mentioned. A block may have 1 type and may have 2 or more types of structural units derived from the vinyl monomer which has an acidic group.

As a vinyl monomer which has the said acidic group, at least 1 sort (s) chosen from the vinyl monomer which has a carboxy group, the vinyl monomer which has a sulfonic acid group, or the vinyl monomer which has a phosphoric acid group is preferable. Among these, Preferably, it is at least 1 sort (s) chosen from the (meth) acryl monomer which has a carboxy group, the (meth) acryl monomer which has a sulfonic acid group, or the (meth) acryl monomer which has a phosphoric acid group.

As a vinyl monomer which has a carboxy group, (meth) acrylic acid; Vinyl monomer which has hydroxyl groups, such as 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, and 2- (meth) acryloyloxyethyl phthalate (preferably hydroxy Oxyalkyl (meth) acrylate) and an acid anhydride such as maleic anhydride, succinic anhydride and phthalic anhydride; Crotonic acid, maleic acid, itaconic acid, etc. are mentioned.

Examples of the vinyl monomer having a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, disulfonic acid ethyl (meth) acrylate, methylpropylsulfonic acid (meth) acrylamide, and sulfonic acid ethyl (meth) acrylamide.

(Meth) acrylic acid 2- (phosphonooxy) ethyl etc. are mentioned as a vinyl monomer which has a phosphoric acid group.

As for the content rate of 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, More preferably, it is 5 mass% or more, More preferably, it is 7 mass% or more, 20 mass% The following is preferable, More preferably, it is 18 mass% or less, More preferably, it is 16 mass% or less. When the content rate of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with alkali is increased in alkali development, and when the content is 20% by mass or less, the hydrophilicity is not too high, and the pixels formed are obfuscated. It can suppress deterioration.

The said A block may have structural units other than the structural unit derived from the vinyl monomer which has an acidic group. The other structural unit that can be included in the A block is not particularly limited as long as it is formed of a vinyl monomer copolymerizable with both a vinyl monomer having an acid group and a vinyl monomer forming a B block described later. The vinyl monomer which can form the other structural unit of A block may be used independently, and may use 2 or more types together.

As a specific example of the vinyl monomer which can form the other structural unit of A block, (alpha) -olefin, an aromatic vinyl monomer, the vinyl monomer containing a heterocyclic ring, vinyl amide, vinyl carboxylate, dienes, (meth) acryl monomer, etc. Can be mentioned. These vinyl monomers may have a hydroxyl group and an epoxy group.

1-hexene, 1-octene, 1-decene etc. are mentioned as an alpha olefin.

As an aromatic vinyl monomer, styrene, (alpha) -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinyl naphthalene, etc. are mentioned. .

Examples of the vinyl monomer containing a hetero ring include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, and 4-vinylpyridine.

Examples of the vinylamides include N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam, and the like.

Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.

Examples of the dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and the like.

As a (meth) acryl monomer, (meth) acrylate which has a linear alkyl group (straight alkyl group or branched alkyl group); (Meth) acrylate which has a cyclic alkyl group (monocyclic structure); (Meth) acrylate which has an aromatic ring group; (Meth) acrylamide; (Meth) acrylates having polyethylene glycol structural units; (Meth) acrylate which has a hydroxyl group; Caprolactone adducts of (meth) acrylates having a hydroxyl group; (Meth) acrylate which has an alkoxy group; (Meth) acrylate etc. which have a cyclic ether group are mentioned.

As (meth) acrylate which has a linear alkyl group, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acryl The rate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. are mentioned. Cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, etc. are mentioned as (meth) acrylate which has a cyclic alkyl group. As (meth) acrylate which has an aromatic ring group, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. are mentioned.

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N- dimethyl (meth) acrylamide, etc. are mentioned. As (meth) acrylate which has a polyethyleneglycol structural unit, polyethyleneglycol (n = 1-5) methyl ether (meth) acrylate, polyethyleneglycol (n = 1-5) ethyl ether (meth) acrylate, polyethyleneglycol (n = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1-5) ethyl ether (meth) acrylate And polypropylene glycol (n = 1 to 5) propyl ether (meth) acrylate.

As (meth) acrylate which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates, such as (meth) acrylate, etc. are mentioned.

As a caprolactone addition product of (meth) acrylate which has a hydroxyl group, 1 mol of adducts of caprolactone of 2-hydroxyethyl (meth) acrylate, and 2 mol addition products of caprolactone of 2-hydroxyethyl (meth) acrylate , 3 mol addition product of caprolactone of 2-hydroxyethyl (meth) acrylate, 4 mol addition product of caprolactone of 2-hydroxyethyl (meth) acrylate, 5 mol addition of caprolactone of 2-hydroxyethyl (meth) acrylate Water and the like.

As (meth) acrylate which has an alkoxy group, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. are mentioned.

As (meth) acrylate which has a cyclic ether group, glycidyl (meth) acrylate, (meth) acrylic acid tetrahydrofurfuryl, (meth) acryloyl morpholine, (meth) acrylic acid 2- (4-morpholine) Il) ethyl, (3-ethyloxetan-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, Cyclic trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate, and the like.

As for the vinyl monomer which can form the other structural unit which can be contained in A block, a (meth) acryl monomer is preferable, (meth) acrylate which has a linear alkyl group, (meth) acrylate which has an aromatic ring group, and a polyethyleneglycol structure At least selected from the group consisting of (meth) acrylates having units, (meth) acrylates having hydroxy groups, caprolactone adducts of (meth) acrylates having hydroxy groups, and (meth) acrylates having cyclic ether groups It is more preferable that it is 1 type. 1 type (s) or 2 or more types can be used for the said vinyl monomer which can be used by A block, respectively.

A structure is derived from at least one vinyl monomer selected from the group consisting of a (meth) acrylate having a chain alkyl group, a (meth) acrylate having a cyclic alkyl group, and a (meth) acrylate having an aromatic ring group When it has a unit, 30 mass% or more is preferable in 100 mass% of A blocks, and, as for the sum total content rate of these structural units, More preferably, it is 35 mass% or more, More preferably, it is 40 mass% or more, 98 mass% The following is preferable, More preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less.

A block has a (meth) acrylamide, the (meth) acrylate which has a polyethyleneglycol structural unit, the (meth) acrylate which has a hydroxyl group, the caprolactone addition product of the (meth) acrylate which has a hydroxyl group, and an alkoxy group When it has a structural unit derived from at least 1 sort (s) of vinyl monomer chosen from the group which consists of (meth) acrylate and the (meth) acrylate which has a cyclic ether group, the total content rate of these structural units is 100 mass of A blocks. 2 mass% or more is preferable in%, More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, 70 mass% or less is preferable, More preferably, it is 65 mass% or less, More preferably, It is 60 mass% or less.

Moreover, it is preferable that A block does not have an amino group. That is, it is preferable that the vinyl monomer which comprises A block does not contain the vinyl monomer which has an amino group. When a large amount of amino groups exists in A block, when used as a pigment dispersant, a pigment will adsorb | suck to both A block and B block, and the dispersion performance of a pigment will fall. As for the content rate of the structural unit derived from the vinyl monomer which has an amino group in A block, 2 mass% or less is preferable, More preferably, it is 1 mass% or less, More preferably, it is 0.1 mass% or less, Most preferably, 0 mass% to be.

When 2 or more types of structural units are contained in A block, the various structural units contained in A block may be contained in any form of random copolymerization, block copolymerization, etc. in A block, and the form of random copolymerization from a uniformity viewpoint. It is preferable that it contains. For example, A block may be formed of the copolymer of the structural unit which consists of a1 blocks, and the structural unit which consists of a2 blocks.

(1.2 B blocks)

The B block is a polymer block having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). Since the B block has a quaternary ammonium base group in addition to the tertiary amino group, it is considered to have high affinity with the pigment.

(1.2.1 structural unit represented by General Formula (1))

The structural unit represented by General formula (1) has a quaternary ammonium salt in a structure, At least selected from the group which consists of an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, and an aromatic carboxylic acid anion as its anion component. It has one kind. 1 type may be sufficient as the structural unit represented by General formula (1) in B block, and it may have 2 or more types.

[In Formula (1), R <^11> , R <^12> and R <^13> respectively independently represents the 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. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents at least one member selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions.]

The linear hydrocarbon group represented by R ^{11 to} R ¹³ includes both a straight chain and a branched chain. With a substituent group having a hydrocarbon chain represented by the above R ^{11 ~} R ^13, there may be mentioned a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H _5), a hydroxyl group or the like. As a substituent which the cyclic hydrocarbon group represented by said R <^11> -R <^13> has, a linear alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, etc. are mentioned.

As group represented by said R <^11> -R <^13> , the C1-C4 alkyl group which may have a substituent, and the C7-C16 aralkyl group which may have a substituent are preferable, and a methyl group, an ethyl group, a propyl group, and a benzyl group ( -CH ₂ C ₆ H ₅ ) is more preferred.

As a cyclic structure which two or more of said R <^11> -R <^13> combines with each other, the 5-7 membered nitrogen-containing heterocyclic ring or the condensed ring which these two condensed is mentioned, for example. It is preferable that the said nitrogen-containing heterocycle does not have aromaticity, and a saturated ring is more preferable. Specifically, the structure represented by following formula (11-1), (11-2), (11-3) is mentioned.

[In General Formula (11-1), (11-2), (11-3), R ⁶¹ is either of R ^{11 to} R ¹³ . R ⁶² represents an alkyl group having 1 to 6 carbon atoms. l represents the integer of 0-5. m represents the integer of 0-4. n represents the integer of 0-4. When l is 2-5, m is 2-4, n is 2-4, two or more R <^62> may be same or different.]

In general formula (1), as a bivalent coupling group X <^1> , a methylene group, a C2-C10 alkylene group, an arylene group, -CONH-R <^15> -group, -COO-R <^16> -group [However, R <^15> and R <^16> is a single bond, a methylene group, a C2-C10 alkylene group, or a C2-C10 ether group (alkyloxyalkyl group). The divalent linking group X ¹ is preferably a -COO-R ¹⁶ -group, and more preferably a -COO-R ¹⁷ -group (wherein R ¹⁷ is a methylene group or an alkylene group having 2 to 4 carbon atoms).

Y <^{-> which} is a counter ion in the said General formula (1) represents at least 1 sort (s) chosen from the group which consists of an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, and an aromatic carboxylic acid anion. Among these, Y <^{-> which} is a counter ion is preferable an aromatic dicarboxylic acid imide anion and an aromatic sulfonic acid anion.

An aromatic dicarboxylic acid imide anion is an anion of aromatic dicarboxylic acid imide, and removes protons from the nitrogen which comprises dicarbodiimide. Aromatic dicarboxylic acid imide has an imide group (-C (= O) NHC (= O)-) which bonds directly to an aromatic ring and an aromatic ring in a molecule | numerator. Both ends of the imide group may be bonded to one aromatic ring, or may be bonded to different aromatic rings, respectively. As aromatic dicarboxylic acid imide anion, what is represented by General formula (12) is preferable.

[In General Formula (12), Ring A represents an aromatic ring which may have a substituent.]

In General formula (12), the aromatic ring which comprises ring A is ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned.

Examples of the aromatic dicarboxylic acid imide anion include 1,3-dioxo-1,3-dihydro-2H-isoindole-2-ide (formula (12-1)); 1,3-dioxo-1,3-dihydro-2H-benzo [f] isoindole-2-ide (formula (12-2)); 1,3-dioxo-1,3-dihydro-2H-benzo [g] isoindole-2-ide (formula (12-3)); 5-phenyl-1,3-dioxo-1,3-dihydro-2H-isoindole-2-ide (formula (12-4)); 1,3-dioxo-1,3-dihydro-2H-naphtho [2,3-f] isoindole-2-ide (formula (12-5)); 1,3-dioxo-1,3-dihydro-2H-naphtho [2,3-g] isoindole-2-ide (formula (12-6)); 1,3-dioxo-1,3-dihydro-2H-dibenzo [e, g] isoindole-2-ide (formula (12-7)); Etc. can be mentioned

An aromatic sulfonic acid anion is an anion of aromatic sulfonic acid. Aromatic sulfonic acid has an aromatic ring and a sulfonic acid group directly bonded to this aromatic ring in a molecule. As an aromatic sulfonic acid anion, what is represented by following formula (13) is preferable.

[In General formula (13), Ar represents the aromatic ring which may have a substituent.]

In General formula (13), the aromatic ring which comprises Ar is a ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned.

As an aromatic sulfonic acid anion, Benzenesulfonic acid anion (formula (13-1)); 1-naphthalenesulfonic acid anion (formula (13-2)); 2-naphthalenesulfonic acid anion (formula (13-3)); 4-biphenylsulfonic acid anion (formula (13-4)); 2-anthracenesulfonic acid anion (formula (13-5)); 1-anthracenesulfonic acid anion (formula (13-6)); 3-phenanthrenesulfonic acid anion (formula (13-7)); p-styrenesulfonic acid anion (formula (13-8)); p-toluenesulfonic acid anion (formula (13-9)) etc. are mentioned.

An aromatic phosphonic acid anion is an anion of aromatic phosphonic acid. Aromatic phosphonic acid has an aromatic ring and the phosphonic acid group which couple | bonded directly with this aromatic ring in a molecule | numerator. As an aromatic phosphonic acid anion, what is represented by following formula (14) is preferable.

[In General formula (14), Ar represents the aromatic ring which may have a substituent.]

In General formula (14), the aromatic ring which comprises Ar is a ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned.

As an aromatic phosphonic acid anion, Benzene phosphonic acid anion (formula (14-1)); 1-naphthalenephosphonic acid anion (formula (14-2)); 2-naphthalenephosphonic acid anion (formula (14-3)); 4-biphenylphosphonic acid anion (formula (14-4)); 2-anthracenephosphonic acid anion (formula (14-5)); 1-anthracenephosphonic acid anion (formula (14-6)); 3-phenanthrenephosphonic acid anion (formula (14-7)); Etc. can be mentioned.

An aromatic carboxylic acid anion is an anion of aromatic carboxylic acid. Aromatic carboxylic acid has an aromatic ring and the carboxy group which couple | bonded directly with this aromatic ring in a molecule | numerator. As an aromatic carboxylic acid anion, what is represented by following formula (15) is preferable.

[In General formula (15), Ar represents the aromatic ring which may have a substituent.]

In General formula (15), the aromatic ring which comprises Ar is a ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned.

As an aromatic carboxylic acid anion, a benzoic acid anion (formula (15-1)); 1-naphthalenecarboxylic acid anion (formula (15-2)); 2-naphthalenecarboxylic acid anion (formula (15-3)); 4-biphenylcarboxylic acid anion (formula (15-4)); 2-anthracenecarboxylic acid anion (formula (15-5)); 1-anthracenecarboxylic acid anion (formula (15-6)); 3-phenanthrenecarboxylic acid anion (formula (15-7)); p-styrenecarboxylic acid anion (formula (15-8)); p-toluenecarboxylic acid anion (formula (15-9)), etc. are mentioned.

As for the content rate of the structural unit represented by General formula (1), 30 mass% or more is preferable in 100 mass% of B blocks, More preferably, it is 35 mass% or more, More preferably, it is 40 mass% or more, and 85 mass% The following is preferable, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. It is thought that it has high affinity with a pigment by making content rate of the structural unit represented by General formula (1) into this range.

(1.2.2 structural unit represented by formula (2))

The structural unit represented by General formula (2) has a tertiary amine structure. 1 type may be sufficient as the structural unit represented by General formula (2) in B block, and it may have 2 or more types.

[In formula (2), R <^21> and R <^22> represents the linear or cyclic hydrocarbon group which may respectively have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

Both linear and branched chains are contained in the linear hydrocarbon group represented by R ²¹ or R ²² . As a substituent which the linear hydrocarbon group represented by said R <^21> or R <^22> has, a halogen group, an alkoxy group, a benzoyl group, a hydroxyl group, etc. are mentioned. As a substituent which the cyclic hydrocarbon group represented by said R <^21> or R <^22> has, a linear alkyl group, a halogen group, an alkoxy group, a hydroxyl group, etc. are mentioned.

As group represented by said R <^21> or R <^22> , the C1-C4 alkyl group which may have a substituent, and the C7-C16 aralkyl group which may have a substituent are preferable, and a methyl group, an ethyl group, a propyl group, and a benzyl group are more preferable. desirable.

As a cyclic structure which said R <^21> or R <^22> combines with each other, the 5-7 membered nitrogen-containing heterocyclic ring or the condensed ring which these two condensate is mentioned, for example. It is preferable that the said nitrogen-containing heterocycle does not have aromaticity, and a saturated ring is more preferable. Specifically, the structure represented by following formula (21-1), (21-2), (21-3) is mentioned.

[In General formula (21-1), (21-2), (21-3), R <^71> represents a C1-C6 alkyl group. l represents the integer of 0-5. m represents the integer of 0-4. n represents the integer of 0-4. When l is 2-5, m is 2-4, and n is 2-4, two or more R ⁷¹ may be same or different.]

In the general formula (2), as the divalent linking group X ² , for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a -CONH-R ²⁴ -group, and a -COO-R ²⁵ -group [ , R ²⁴ and R ²⁵ are a single bond, a methylene group, an alkylene group of 2 to 10 carbon atoms or an ether group (alkyloxyalkyl group) of 2 to 10 carbon atoms], etc., and preferably -COO-R ^25- . the group, -COO-R ²⁶ - a group - only, R ²⁶ is a methylene group, an alkylene group having 2 to 4 is more preferred.

As for the content rate of the structural unit represented by General formula (2), 15 mass% or more is preferable in 100 mass% of B blocks, More preferably, it is 20 mass% or more, More preferably, it is 25 mass% or more, 70 mass% The following is preferable, More preferably, it is 65 mass% or less, More preferably, it is 60 mass% or less. It is thought that it has high affinity with a pigment by making content rate of the structural unit represented by General formula (2) into this range.

B block may be only the structural unit represented by General formula (1), and the structural unit represented by General formula (2), and the other structural unit may be contained. From a viewpoint of maintaining affinity with a pigment, 80 mass% or more is preferable and, as for the total content rate of the structural unit represented by General formula (1) in B-block, and the structural unit represented by General formula (2), it is more preferable. Preferably it is 90 mass% or more, More preferably, it is 95 mass% or more. Moreover, it is preferable that B block does not contain substantially the structural unit derived from the vinyl monomer which has the acidic group which A block has. That is, 5 mass% or less is preferable in 100 mass% of B blocks, and, as for the content rate of the structural unit derived from the vinyl monomer which has an acidic group which A block has, 2 mass% or less is more preferable.

As a specific example of the vinyl monomer which can form the other structural unit of B block, the thing similar to what was illustrated as a specific example of the monomer of vinyl which can form the other structural unit of A block is mentioned.

When 2 or more types of structural units are contained in a B block, the various structural units contained in a B block may be contained in any form, such as random copolymerization and block copolymerization, in a B block, and the form of a random copolymerization from a uniformity viewpoint. It is preferable that it contains. For example, the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.

(1.3 block copolymer)

It is preferable that the structure of the block copolymer of this invention is a linear block copolymer. The linear block copolymer may be any structure (array), but in terms of the physical properties of the linear block copolymer or the physical properties of the composition, when the A block is represented by A and the B block is represented by B, the (AB) _m type, It is preferable that it is a copolymer which has at least 1 sort (s) of structure chosen from the group which consists of (AB) _m- A type and (BA) _m- B type (m is an integer of 1 or more, for example, 1-3). Among these, it is preferable that it is the diblock copolymer represented by AB from the viewpoint of the handleability at the time of processing, and the physical property of a composition. By constructing the diblock copolymer represented by AB, it has a structural unit derived from the vinyl monomer which has an acidic group in A block, a structural unit derived from the vinyl monomer which has a tertiary amino group in B block, and a quaternary ammonium base group. The structural unit derived from a vinyl monomer is localized, and it is thought that it can work efficiently with a pigment, a solvent, and binder resin (alkali-soluble resin) efficiently.

As for the content rate of A block, 35 mass% or more is preferable in 100 mass% of whole block copolymers, More preferably, it is 40 mass% or more, More preferably, it is 45 mass% or more, 85 mass% or less is more, Preferably it is 80 mass% or less, More preferably, it is 75 mass% or less. As for the content rate of B block, 15 mass% or more is preferable in 100 mass% of whole block copolymers, More preferably, it is 20 mass% or more, More preferably, it is 25 mass% or more, 65 mass% or less is more, Preferably it is 60 mass% or less, More preferably, it is 55 mass% or less. By adjusting the content rate of A block and B block in the said range, the heat resistance and the dispersing performance at the time of using it as a dispersing agent can be balanced well.

<First Composition of Two Block Copolymer>

The 1st composition of this invention contains the said block copolymer. The said 1st composition contains other components other than the said block copolymer. As said other component, the impurity resulting from the manufacturing method of a block copolymer is mentioned. For example, when the quaternization agent mentioned later, at least 1 sort (s) of alkali metal salt chosen from the group which consists of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid are used for manufacture of a block copolymer, the said quaternary Alkali metal components derived from alkali metal salts, such as a halogen component derived from a topical agent and aromatic dicarboxylic acid imide, are mentioned. In addition, the 1st composition removes impurities, such as the salt (the salt of the halogen component derived from the said quaternization agent, and the alkali metal component derived from alkali metal salts, such as aromatic dicarboxylic acid imide), by filtration. desirable.

The molecular weight of the block copolymer contained in the said 1st composition is measured by the gel permeation chromatography (henceforth "GPC") method. 5000 or more are preferable, as for the weight average molecular weight (Mw) of the said block copolymer, More preferably, it is 6000 or more, More preferably, it is 7000 or more, 15000 or less are preferable, More preferably, it is 12000 or less, More preferably, 10000 or less. When the weight average molecular weight is in the above range, the dispersion performance when used as a dispersant becomes better.

It is preferable that it is 2.0 or less, and, as for the molecular weight distribution (PDI) of the block copolymer contained in a said 1st composition, it is more preferable that it is 1.6 or less. In addition, in this invention, molecular weight distribution (PDI) is calculated | required by (weight average molecular weight (Mw) of a block copolymer) / (number average molecular weight (Mn) of a block copolymer). The smaller the PDI, the narrower the molecular weight distribution and the more uniform the molecular weight, and when the value is 1.0, the narrowest the molecular weight distribution is. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, one having a small molecular weight or one having a large molecular weight is included.

The amine titer of the first composition is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and 200 mgKOH / g or less from the viewpoint of adsorptivity and pigment dispersibility to the pigment. It is preferable, More preferably, it is 150 mgKOH / g or less, More preferably, it is 100 mgKOH / g or less.

As for the acid value of the said 1st composition, 5 mgKOH / g or more is preferable, More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, 50 mgKOH / g or less is preferable, More preferably, 40 mgKOH / g or less More preferably, it is 35 mgKOH / g or less. By setting the acid value to this range, the affinity of the pigment of the block copolymer can be satisfactorily functioned with binder resin (alkali-soluble resin).

<2nd composition of a 3 block copolymer>

The second composition of the present invention is obtained by washing with water and drying the first composition. As for the 2nd composition after water washing and drying, content of the salt (the salt of the alkali component derived from the halogen component derived from the said quaternization agent, and alkali metal salts, such as aromatic dicarboxylic acid imide), is reduced. Moreover, also about a 2nd composition, the impurity resulting from the manufacturing method of a block copolymer is contained similarly to the said 1st composition. The said 1st composition is a composition containing the said block copolymer, The reaction liquid at the time of synthesize | combining a block copolymer is also included.

The block copolymer contained in the said 2nd composition may or may not have a structural unit represented by General formula (1). Moreover, the said 2nd composition contains other components other than a block copolymer. As said other component, aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid are mentioned. These ice aromatic dicarboxylic acid imides, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid may be an anion or an alkali metal salt may be sufficient as them.

The molecular weight of the block copolymer contained in the said 2nd composition is measured by GPC method. 5000 or more are preferable, as for the weight average molecular weight (Mw) of the said block copolymer, More preferably, it is 6000 or more, More preferably, it is 7000 or more, 15000 or less are preferable, More preferably, it is 12000 or less, More preferably, 10000 or less. When the weight average molecular weight is in the above range, the dispersion performance when used as a dispersant becomes better.

It is preferable that it is 2.0 or less, and, as for the molecular weight distribution (PDI) of the block copolymer contained in a said 2nd composition, it is more preferable that it is 1.6 or less. When molecular weight distribution (PDI) of a block copolymer exceeds 2.0, the thing with small molecular weight or the one with large molecular weight will be included.

The amine titer of the second composition is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and 200 mgKOH / g or less from the viewpoint of adsorptivity and pigment dispersibility to the pigment. It is preferable, More preferably, it is 150 mgKOH / g or less, More preferably, it is 100 mgKOH / g or less.

As for the acid value of the said 2nd composition, 5 mgKOH / g or more is preferable, More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, 50 mgKOH / g or less is preferable, More preferably, 40 mgKOH / g Or less, more preferably 35 mg KOH / g or less.

It is preferable that content of a halogen anion of the said 2nd composition is 8000 ppm or less, More preferably, it is 6000 ppm or less, More preferably, it is 4000 ppm or less.

<Method for producing 4-block copolymer>

The manufacturing method of the block copolymer of this onset is represented by the A block containing the structural unit derived from the vinyl monomer which has an acidic group, the structural unit represented by General formula (2) mentioned later, and General formula (3) mentioned later. (A) preparing a precursor of the block copolymer which has a B block containing the structural unit used; At least one alkali metal salt selected from the group consisting of an aromatic dicarboxylic acid imide, an aromatic sulfonic acid, an aromatic phosphonic acid and an aromatic carboxylic acid is applied to the precursor of the block copolymer obtained in the step (A) to obtain a block copolymer. Process (B); It is characterized by the above-mentioned. In addition, in this invention, a "precursor of a block copolymer" means the block copolymer before anion exchange.

(4.1 Process (A))

In the said process (A), the precursor of a block copolymer is prepared. The precursor of the block copolymer includes an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B containing a structural unit represented by the general formula (2) and a structural unit represented by the general formula (3). Have a block.

[In formula (2), R <^21> and R <^22> represents the linear or cyclic hydrocarbon group which may respectively have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

R <^21> -R <^23> and X <^2> in Formula (2) are the same as described in description of said (B block).

[In Formula (3), R <^31> , R <^32> and R <^33> respectively independently represents the linear or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ^- represents a halogen anion.]

The linear hydrocarbon group represented by the above R ^{31 to} R ³³ includes both linear and branched chains. As a substituent which the linear hydrocarbon group represented by said R <^31> -R ³³ has, a halogen group, 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> -R ³³ has, a linear alkyl group, a halogen group, an alkoxy group, a hydroxyl group, etc. are mentioned.

As group represented by said R <^31> -R <^33> , the C1-C4 alkyl group which may have a substituent, and the C7-C16 aralkyl group which may have a substituent are preferable, and a methyl group, an ethyl group, a propyl group, and a benzyl group are more preferable. desirable.

As a cyclic structure which two or more of said R <^31> -R <^33> couple | bonds with each other, the 5-7 membered ring-containing nitrogen-containing heterocyclic ring or the condensed ring which these two condensed is mentioned, for example. It is preferable that the said nitrogen-containing heterocycle does not have aromaticity, and a saturated ring is more preferable. Specifically, the structure represented by following formula (31-1), (31-2), (31-3) is mentioned.

[In Formulas (31-1), (31-2) and (31-3), R ⁸¹ is any one of R ^{31 to} R ³³ . R ⁸² represents an alkyl group having 1 to 6 carbon atoms. l represents the integer of 0-5. m represents the integer of 0-4. n represents the integer of 0-4. When l is 2-5, m is 2-4, n is 2-4, two or more R <^82> may be same or different, respectively.]

In the general formula (3), as the divalent linking group X ³ , for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a -CONH-R ³⁵ -group, a -COO-R ³⁶ -group [ Provided that R ³⁵ and R ³⁶ are a single bond, a methylene group, a C2-C10 alkylene group or a C2-C10 ether group (alkyloxyalkyl group); and the like, preferably -COO-R ^36. It is a -group, and -COO-R ³⁷ -group (wherein R ³⁷ is a methylene group and a C2-C4 alkylene group) is more preferable.

X <^-> includes halogen anions, such as chloride ion, bromide ion, and iodide ion, Preferably it is chloride ion.

(4.1.1 A block)

In the said process (A), A block is obtained by superposing | polymerizing the monomer composition containing the vinyl monomer which has an acidic group, for example.

As a vinyl monomer which has an acidic group used at the said process (A), the above-mentioned thing can be used, At least 1 sort (s) chosen from the vinyl monomer which has a carboxy group, the vinyl monomer which has a sulfonic acid group, or the vinyl monomer which has a phosphoric acid group is preferable. Moreover, in addition to the vinyl monomer which has an acidic group, you may mix | blend the vinyl monomer which can form the other structural unit of the above-mentioned A block with the monomer composition for A blocks.

(4.1.2 B block)

In the said process (A), B block contains the vinyl monomer which can form the structural unit represented by General formula (2), and the vinyl monomer which can form the structural unit represented by General formula (3). A method of polymerizing a monomer composition; After superposing | polymerizing the monomer composition containing the vinyl monomer which can form the structural unit represented by General formula (2), quaternizing the tertiary amine structure of one part of the structural unit represented by General formula (2) in the obtained polymer. How to do it.

Although it does not specifically limit as a vinyl monomer which can form the structural unit represented by the said General formula (2), For example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and dimethylaminobutyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, etc. are mentioned. The vinyl monomer which can form the structural unit represented by the said General formula (2) may be used independently, and may use 2 or more types together.

Although it does not specifically limit as a vinyl monomer which can form the structural unit represented by the said General formula (3), For example, (meth) acryloyloxyethyl trimethylammonium chloride and (meth) acryloyloxypropyl trimethyl Ammonium chloride, (meth) acryloyloxybutyltrimethylammonium chloride, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxypropylbenzyldimethylammonium chloride, (meth) acryloyloxybutylbenzyl Dimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride, (meth) acryloyloxypropylbenzyldiethylammonium chloride, (meth) acryloyloxybutylbenzyldiethylammonium chloride; (Meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium bromide, ( Meta) acryloyloxypropylbenzyldimethylammonium bromide, (meth) acryloyloxybutylbenzyldimethylammonium bromide, (meth) acryloyloxyethylbenzyldiethylammonium bromide, (meth) acryloyloxypropylbenzyldiethyl Ammonium bromide, (meth) acryloyloxybutylbenzyldiethylammonium bromide; (Meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) acryloyloxybutyltrimethylammonium iodide, (meth) acryloyloxyethyl Benzyldimethylammonium iodide, (meth) acryloyloxypropylbenzyldimethylammonium iodide, (meth) acryloyloxybutylbenzyldimethylammonium iodide, (meth) acryloyloxyethylbenzyldiethylammonium i Amide, (meth) acryloyloxypropylbenzyldiethylammonium iodide, (meth) acryloyloxybutylbenzyldiethylammonium iodide; (Meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxyethylbenzyldimethylammonium Fluoride, (meth) acryloyloxypropylbenzyldimethylammonium fluoride, (meth) acryloyloxybutylbenzyldimethylammonium fluoride, (meth) acryloyloxyethylbenzyldiethylammonium fluoride, (meth) acrylic Royloxypropyl benzyl diethyl ammonium fluoride and (meth) acryloyloxybutyl benzyl diethyl ammonium fluoride are mentioned. The vinyl monomer which can form the structural unit represented by the said General formula (3) may be used independently, and may use 2 or more types together.

Moreover, when quaternizing the tertiary amine structure of the structural unit represented by General formula (2), As a quaternizing agent, Alkyl halides, such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; Aralkyl halides, such as benzyl chloride, benzyl bromide, and benzyl iodide, are mentioned. Among them, aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide are preferable, and benzyl chloride is more preferable. The alkyl group and aralkyl group derived from a quaternization agent are introduce | transduced into the structure after quaternization. Therefore, the quantity of the structural unit represented by General formula (3) can be estimated by measuring the quantity of the alkyl group and the aralkyl group which were introduce | transduced by quaternization.

(4.1.3 method)

As said process (A), the method of manufacturing A block first, and polymerizing the monomer of a B block to A block; Preparing a B block first, and then polymerizing the monomers of the A block into the B block; Preparing the A block and the B block separately, and then coupling the A block and the B block; A block is first prepared, the monomer composition containing a vinyl monomer capable of forming the structural unit represented by the general formula (2) in the A block is polymerized, and the structural unit represented by the general formula (2) in the obtained polymer A method of quaternizing some tertiary amine structures; The monomeric unit containing the vinyl monomer which can form the structural unit represented by General formula (2) is superposed | polymerized, the monomer of A block is superposed | polymerized on this polymer, and the structural unit represented by General formula (2) in the obtained polymer A method of quaternizing a tertiary amine structure of a portion of the; A tertiary amine structure of a part of the structural units represented by the general formula (2) in the obtained polymerized product after the production of the block having the structural unit represented by the A block and the general formula (2) separately and coupling these blocks. How to quaternize; may be mentioned.

(4.1.4 Living Radical Polymerization)

Although the polymerization method is not specifically limited, Living radical polymerization is preferable. That is, as said 1st block copolymer, what superposed | polymerized using living radical polymerization is preferable. In the conventional radical polymerization method, not only the initiation reaction and the growth reaction, but also the stop reaction and the chain transfer reaction cause loss of activity at the growth end, and tend to be a mixture of polymers of various molecular weights and heterogeneous compositions. Since the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, it is difficult to cause a stop reaction or a chain transfer, and the growth terminal is grown without loss of activity, so that precise control of the molecular weight distribution and uniform composition are achieved. It is preferable at the point which manufacture of a polymer is easy.

The living radical polymerization method includes a method using a transition metal catalyst (ATRP method) in accordance with a difference in a method of stabilizing a polymerization growth terminal; A method using a sulfur-based reversible chain transfer agent (RAFT method); The method using an organic tellurium compound (TERP method), etc. are mentioned. Since the ATRP method uses an amine complex, it may not be used unless the acidic group of the vinyl monomer having an acidic group is protected. In the case of using multiple monomers, the RAFT method is less likely to have a low molecular weight distribution, and there may be a defect such as sulfur odor or coloring. Among these methods, the TERP method is preferably used in view of the variety of monomers that can be used, 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 polymerization initiator. For example, International Publication No. 2004/14848, International Publication No. 2004/14962, International Publication Agent The method described in 2004/072126 and International Publication 2004/096870.

The following (a)-(d) is mentioned as a specific polymerization method of TERP method.

(a) A method of polymerizing a vinyl monomer using an organic tellurium compound represented by the general formula (4).

(b) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4) and an azo polymerization initiator.

(c) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4) and an organic ditellurium compound represented by the general formula (5).

(d) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4), an azo polymerization initiator and an organic ditellurium compound represented by the general formula (5).

[In General formula (4), R <^41> represents a C1-C8 alkyl group, 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, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or propargyl group having 1 to 8 carbon atoms.]

[In General formula (5), R ⁴¹ represents a C1-C8 alkyl group, an aryl group, or an aromatic heterocyclic group.]

Group represented by R <^41> is a C1-C8 alkyl group, an aryl group, or an aromatic heterocyclic group, and is as follows specifically ,.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, Cyclic alkyl groups, such as a linear or branched alkyl group, such as an octyl group, and a cyclohexyl group, are mentioned. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

A phenyl group, a naphthyl group, etc. are mentioned as an aryl group.

As an aromatic heterocyclic group, a pyridyl group, a furyl group, thienyl group, etc. are 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.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, Cyclic alkyl groups, such as a linear or branched alkyl group, such as an octyl group, and a cyclohexyl group, etc. are mentioned. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

The group represented by R ⁴⁴ is an alkyl group having 1 to 8 carbon atoms, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or propargyl group. As follows.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, Cyclic alkyl groups, such as a linear or branched alkyl group, such as an octyl group, and a cyclohexyl group, etc. are mentioned. Preferably it is a C1-C4 linear or branched alkyl group, More preferably, it is a methyl group or an ethyl group.

A phenyl group, a naphthyl group, etc. are mentioned as an aryl group. Preferably it is a phenyl group.

As a substituted aryl group, the phenyl group which has a substituent, the naphthyl group which has a substituent, etc. are mentioned. As a substituent of the aryl group which has a substituent, For example, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, the carbonyl containing group represented by -COR ⁴⁴¹ ( ^R441 has C1-C8) Alkyl group, aryl group, alkoxy group or aryloxy group having 1 to 8 carbon atoms), sulfonyl group, trifluoromethyl group and the like. Moreover, it is good to substitute one or two of these substituents.

As an aromatic heterocyclic group, a pyridyl group, a furyl group, thienyl group, etc. are mentioned.

As an alkoxy group, the group which the C1-C8 alkyl group couple | bonded with the oxygen atom is preferable, For example, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butok A time period, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

As an acyl group, an acetyl group, a propionyl group, a benzoyl group, etc. are mentioned.

Examples of the amide group include -CONR ⁴⁴²¹ R ⁴⁴²² (R ⁴⁴²¹ and R ⁴⁴²² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).

As the oxycarbonyl group, a group represented by -COOR ⁴⁴³ (R ⁴⁴³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group) is preferable. For example, a carboxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n -Butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, etc. are mentioned. Preferred oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.

As the allyl group, -CR ⁴⁴⁴¹ R ⁴⁴⁴² -CR ⁴⁴⁴³ = CR ⁴⁴⁴⁴ R ⁴⁴⁴⁵ (R ⁴⁴⁴¹ and R ⁴⁴⁴² each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴⁴⁴³ , R ⁴⁴⁴⁴ , and R ⁴⁴⁴⁵ each independently represent hydrogen. It is an atom, a C1-C8 alkyl group, or an aryl group, and each substituent may be connected by the cyclic structure).

Pro Parr long as ^{is, -CR 4451 R 4452 -C≡CR 4453 (} R 4451, R 4452 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴⁴⁵³ represents a hydrogen atom, alkyl group having 1 to 8 carbon atoms, aryl or silyl Can be mentioned.

Specific examples of the organic tellurium compound represented by the general formula (4) include (methylteranylmethyl) benzene, (methylteranylmethyl) naphthalene, ethyl-2-methyl-2-methylteranyl-propionate, and ethyl. -2-methyl-2-n-butylteranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylteranyl-propionate, (2-hydroxyethyl) -2- Methyl-2-methylteranyl-propionate or (3-trimethylsilylpropargyl) -2-methyl-2-methylteranyl-propionate, etc., International Publication 2004/14848, International Publication 2004 / The organic tellurium compound described in 14962, international publication 2004/072126, and international publication 2004/096870 can all be illustrated.

The organic ditellurium compound represented by General formula (5) specifically, has a dimethylditelluride, diethylditelluride, di-n-propyldi telluride, diisopropyldi telluride, dicyclopropyldi telluride , Di-n-butyldi telluride, di-s-butyldi telluride, di-t-butyldi telluride, dicyclobutyldi telluride, diphenyldi telluride, bis- (p-methoxyphenyl) De telluride, bis- (p-aminophenyl) ditelluride, bis- (p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) Ditelluride, dinaphthylditelluride, dipyridylditelluride, etc. can be illustrated.

The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization. For example, 2,2'-azobis (isobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile) (AMBN), 2,2'-azobis (2,4- Dimethylvaleronitrile) (ADVN), 1,1'-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2'-azobisisobutyrate (MAIB), 4,4'-azobis (4-cyanovaleric acid) (ACVA), 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobis (2-methylbutylamide), 2,2 ' -Azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [ 2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2 , 4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2'-azobis (N-butyl-2-methylpropionamide) or 2,2'-azobis (N- Cyclohexyl-2-methylpropionamide) and the like can be exemplified.

In the polymerization step, the azo polymerization initiator is used for the purpose of promoting reaction, molecular weight and molecular weight distribution control to the vinyl monomer and the organic tellurium compound of the general formula (4) in accordance with the type of the vinyl monomer in a vessel substituted with an inert gas. And / or the organic de tellurium compound of the general formula (5) is further mixed. At this time, nitrogen, argon, helium, etc. are mentioned as an inert gas. Argon and nitrogen are preferable.

In the polymerization method of the above (a), (b), (c) and (d), the amount of the vinyl monomer may be appropriately adjusted according to the physical properties of the target copolymer, and usually, the organic ether of the general formula (4) It is preferable to make a vinyl monomer into 5-10000 mol with respect to 1 mol of a rulium compound.

In the polymerization method of (b), when using together the organic tellurium compound of General formula (4) and an azo polymerization initiator, as an usage-amount of an azo polymerization initiator, the organic tellurium compound of General formula (4) is usually It is preferable to make an azo polymerization initiator into 0.01 mol-10 mol with respect to 1 mol.

In the polymerization method of the said (c), when using together the organic tellurium compound of General formula (4) and the organic de tellurium compound of General formula (5), as an usage-amount of the organic de tellurium compound of General formula (5), Usually, it is preferable to make the organic dietelium compound of General formula (5) into 0.01 mol-100 mol with respect to 1 mol of organic tellurium compounds of General formula (4).

In the polymerization method of the said (d), when using together the organic tellurium compound of General formula (4), the organic di tellurium compound of General formula (5), and an azo polymerization initiator together, it is usual to use as an azo polymerization initiator It is preferable to make an azo polymerization initiator into 0.01 mol-100 mol with respect to a total of 1 mol of the organic tellurium compound of General formula (4), and the organic di tellurium compound of General formula (5).

Although polymerization reaction can be performed also without a solvent, you may carry out by stirring the said mixture using the aprotic solvent or the protic solvent generally used for radical polymerization. Aprotic solvents that can be used include, for example, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methylethyl ketone), dioxane, propylene Glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene, and the like. As the protic solvent, for example, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol or diacetone alcohol Etc. can be illustrated.

As the usage-amount of a solvent, what is necessary is just to adjust suitably, For example, 0.01 ml or more is preferable with respect to 1 g of vinyl monomers, More preferably, it is 0.05 ml or more, More preferably, it is 0.1 ml or more, 50 ml or less is more preferable Preferably it is 10 ml or less, More preferably, it is 1 ml or less.

What is necessary is just to adjust reaction temperature and reaction time suitably according to the molecular weight distribution of the molecular weight black of the copolymer obtained, Usually, it stirs at 0-150 degreeC for 1 minute-100 hours. The TERP method can obtain high yield and precise molecular weight distribution even at a low polymerization temperature and a short polymerization time. At this time, although a pressure is normally performed at normal pressure, you may pressurize or depressurize.

After completion | finish of a polymerization reaction, the target copolymer can be isolate | separated by normal separation purification means, removal of a used solvent, a residual vinyl monomer, etc. from the obtained reaction mixture.

The growth terminus of the copolymer obtained by the polymerization reaction is in the form of -TeR ⁴¹ (wherein R ⁴¹ is the same as above), and is actively lost by operation in air after the completion of the polymerization reaction, but the tellurium atom remains There is a case. It is preferable to remove the tellurium atoms because the copolymer in which the tellurium atoms remain at the end is colored or poor in thermal stability.

As a method of removing a tellurium atom, Radical reduction method using a tributylstanan, a thiol compound, etc .; A method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular and polymer adsorbents; A method of adsorbing a metal with an ion exchange resin or the like; A liquid that removes residual tellurium compounds by oxidatively decomposing tellurium atoms at the end of the copolymer by adding a peroxide such as hydrogen peroxide or benzoyl peroxide or by blowing air or oxygen into the system, and washing with water or by using a suitable solvent. Liquid extraction or solid-liquid extraction; Purification method in solution state, such as limit filtration which extracts and removes only the thing below a specific molecular weight; can be used, and can also use combining these methods.

(4.1.5 Grade 4)

As a method of quaternizing the tertiary amine structure of one part of the structural unit represented by General formula (2) in a polymer, the method of making a polymer and a quaternization agent contact is mentioned. Specifically, after superposing | polymerizing the monomer composition containing the vinyl monomer which can form the structural unit represented by General formula (2), the method of adding and stirring a quaternization agent to this reaction liquid is mentioned.

55 degreeC-65 degreeC is preferable, and, as for the temperature of the reaction liquid which adds a quaternization agent, 5 hours-20 hours are preferable. When adding a quaternizing agent, it is also preferable to dilute the reaction liquid after polymerization. As a solvent added for dilution, the solvent which can be used for a polymerization reaction is mentioned, A protic solvent is preferable and methanol is more preferable.

(4.1.6 Precursor of Block Copolymer)

The molecular weight of the precursor of the said block copolymer is measured by GPC method. 5000 or more are preferable, as for the weight average molecular weight (Mw) of the precursor of the said block copolymer, More preferably, it is 6000 or more, More preferably, it is 7000 or more, 15000 or less are preferable, More preferably, it is 12000 or less, More preferably Preferably 10000 or less.

It is preferable that it is 2.0 or less, and, as for the molecular weight distribution (PDI) of the precursor of the said block copolymer, it is more preferable that it is 1.6 or less.

As for the content rate of the A block of the precursor of the said block copolymer, 35 mass% or more is preferable in 100 mass% of whole block copolymers, More preferably, it is 40 mass% or more, More preferably, it is 45 mass% or more, and 85 mass % Or less is preferable, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. As for the content rate of B block of the precursor of the said block copolymer, 15 mass% or more is preferable in 100 mass% of whole block copolymers, More preferably, it is 20 mass% or more, More preferably, it is 25 mass% or more, 65 mass% % Or less is preferable, More preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less.

The amine titer of the precursor of the block copolymer is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more, and 200 mgKOH / g from the viewpoint of adsorptivity and pigment dispersibility to the pigment. g or less is preferable, More preferably, it is 150 mgKOH / g or less, More preferably, it is 100 mgKOH / g or less. The amine number of the precursor of the said block copolymer originates in the structural unit represented by General formula (2).

As for the acid value of the precursor of the said block copolymer, 5 mgKOH / g or more is preferable, More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, 50 mgKOH / g or less is preferable, More preferably, 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less.

(4.2 Process (B))

In the step (B), after completion of the step (A), at least one alkali metal salt selected from the group consisting of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid is applied to the precursor of the obtained block copolymer. To obtain a block copolymer. By the step (B), the halogen anion possessed by the structural unit represented by the general formula (3) can be exchanged (anion exchange) with an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonium ion or an aromatic carboxylic acid anion. .

Alkali metals in at least one alkali metal salt selected from the group consisting of aromatic dicarboxylic acid imides, aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids include lithium, sodium, potassium, rubidium, cesium and francium. Lithium, sodium and potassium are preferred in terms of economic advantages.

As an alkali metal salt of aromatic dicarboxylic acid imide, what is represented by General formula (6) is mentioned, for example.

[In General Formula (6), Ring A represents an aromatic ring which may have a substituent, and M ¹ represents an alkali metal.]

In General formula (6), the aromatic ring which comprises ring A is ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned. Examples of the alkali metal represented by M ¹ include lithium, sodium, potassium, rubidium, cesium, and francium.

As an alkali metal salt of aromatic dicarboxylic acid imide, what is represented by General formula (6-1)-(6-7) is mentioned, for example.

[In General Formulas (6-1) to (6-7), M ¹ represents an alkali metal.]

As an alkali metal salt of aromatic sulfonic acid, what is represented by General formula (7) is mentioned, for example.

[In General formula (7), Ar represents the aromatic ring which may have a substituent, and M <^2> represents an alkali metal. "

In General formula (7), the aromatic ring which comprises Ar is ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned. Examples of the alkali metal represented by M ² include lithium, sodium, potassium, rubidium, cesium, and francium.

As an alkali metal salt of aromatic sulfonic acid, what is represented by General formula (7-1)-(7-9) is mentioned, for example.

[In the formula (7-1) ~ (7-9), M 2 represents an alkali metal;

As an alkali metal salt of aromatic phosphonic acid, what is represented by General formula (8) is mentioned, for example.

[In General formula (8), Ar represents the aromatic ring which may have a substituent, and M <^3> represents an alkali metal.]

In General formula (8), the aromatic ring which comprises Ar is a ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned. Examples of the alkali metal represented by M ³ include lithium, sodium, potassium, rubidium, cesium, and francium.

As an alkali metal salt of aromatic phosphonic acid, what is represented by General formula (8-1)-(8-7) is mentioned, for example.

[In General Formulas (8-1) to (8-7), M ³ represents an alkali metal.]

As an alkali metal salt of aromatic carboxylic acid, what is represented by General formula (9) is mentioned, for example.

[In General Formula (9), Ar represents an aromatic ring which may have a substituent, and M ⁴ represents an alkali metal.]

In General formula (9), the aromatic ring which comprises Ar is a ring structure which has aromaticity. As said aromatic ring, both a monocyclic ring and a condensed ring are contained. As said monocyclic ring, a 5 or 6 membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are suitable. As said condensed ring, 2-5 condensed ring is preferable and a naphthalene ring, anthracene ring, a phenanthrene ring, and an indole ring are suitable. As a substituent which the said aromatic ring may have, a C1-C6 alkyl group, a C6-C14 aryl group, a nitro group, a cyano group, a halogen group, etc. are mentioned. Examples of the alkali metal represented by M ⁴ include lithium, sodium, potassium, rubidium, cesium, and francium.

As an alkali metal salt of aromatic carboxylic acid, what is represented by General formula (9-1)-(9-9) is mentioned, for example.

In the said process (B), the method of making the said alkali metal salt act on the precursor of a block copolymer, The method of adding and stirring the said alkali metal salt to the solution which melt | dissolved the precursor of the said block copolymer is mentioned.

In the said process (B), you may add the said alkali metal salt to the reaction liquid after superposition | polymerization of a process (A). Moreover, it is preferable to isolate the precursor of a block copolymer from the polymerization solution after completion | finish of process (A) from the viewpoint of anion exchange efficiency, and to add the said alkali metal salt to the solution which melt | dissolved this in the fresh solvent.

As a solvent which can melt | dissolve the precursor of the said block copolymer, an aprotic solvent or a protic solvent can be used. Aprotic solvents that can be used include, for example, benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methylethyl ketone), dioxane, propylene Glycol monomethyl ether acetate, chloroform, carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene, and the like. As the protic solvent, for example, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol or diacetone alcohol Etc. can be illustrated.

What is necessary is just to adjust suitably as the usage-amount of the solvent for melt | dissolving the precursor of a block copolymer in a process (B), For example, it is the range of 2 ml-10 ml normally with respect to 1 g of precursors of a block copolymer, Preferably it is 2 ml ~ 5ml is good.

As the usage-amount of the at least 1 sort (s) of alkali metal salt chosen from the group which consists of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid, and aromatic carboxylic acid in a process (B), 0.5 equivalent or more is preferable with respect to a quaternary ammonium group, More preferably, it is 0.9 equivalent or more, 1.1 equivalent or less is preferable, More preferably, it is 1.0 equivalent or less.

In the step (B), the solution temperature when the precursor of the block copolymer is brought into contact with the alkali metal salt is usually 55 ° C to 70 ° C, preferably 55 ° C to 65 ° C, and the stirring time is usually 18 hours to 24 hours. Preferably, 20 hours-22 hours are good.

After completion | finish of reaction, the 1st composition containing a block copolymer is obtained by removing a solvent from a reaction liquid. In addition, the obtained 1st composition removes impurities, such as the salt (the halogen component derived from the said quaternization agent, and the alkali metal component derived from alkali metal salts, such as aromatic dicarboxylic acid imide), by filtration. desirable.

(4.3 process (C))

It is preferable that the manufacturing method of the said block copolymer is equipped with the process (C) of washing the block copolymer obtained at the said process (B). Although the well-known washing | cleaning method can be used as said washing | cleaning method, liquid separation washing | cleaning is preferable. Separation washing | cleaning may be performed about the solution after completion | finish of process (B), About the solution which isolate | separated the 1st composition of a block copolymer from the solution after completion | finish of said process (B), and dissolved the obtained 1st composition in the suitable solvent. You may carry out.

As a specific example of the said liquid separation washing | cleaning, after mixing the solvent and water which melt | dissolved the block copolymer, the separated aqueous layer is taken out. By washing with water, the content of the salt (the salt of the halogen component derived from the quaternizing agent and the alkali metal component derived from an alkali metal salt such as aromatic dicarboxylic acid imide) contained in the first composition can be further reduced. Moreover, it is further effective by repeating liquid separation washing. After liquid separation washing, the 2nd composition of the target block copolymer can be obtained by removing the solvent in which the block copolymer melt | dissolved under reduced pressure.

The solvent of the above-mentioned liquid separation operation may be a solvent capable of dissolving the block copolymer and phase separation from water, and for example, ethyl acetate, butyl acetate, isopropyl acetate, methyl isobutyl ketone, and the like, and these are mixed. You may use it. Moreover, the water used for water washing may contain alcohol etc.

In the liquid separation washing, the amount of water used is preferably 0.1 to 10 times by volume, more preferably 0.5 to 5 times by volume, relative to the solvent phase in which the block copolymer is dissolved. 10 degreeC-60 degreeC is preferable, as for liquid temperature at the time of liquid separation washing, More preferably, it is 30 degreeC-50 degreeC, Especially preferably, it is 35 degreeC-45 degreeC.

<5 Dispersants, Pigment Dispersion Compositions>

The dispersing agent of this invention contains the said block copolymer, a 1st composition, or a 2nd composition as a main component. Moreover, it is preferable that the said dispersing agent consists only substantially of the block copolymer, 1st composition, or 2nd composition of this invention. The pigment dispersion composition of this invention contains the said dispersing agent, a pigment, and a dispersion medium. The kind and particle diameter of the pigment used in this case differ also with the use, and are not specifically limited. The said pigment dispersion composition can be used for a color filter. The block copolymer which characterizes this invention WHEREIN: The tertiary amino group and quaternary ammonium base in the structure (B block) couple | bond strongly with the acidic group of the pigment processed with the acidic pigment or the acidic group containing pigment derivative, and this B block is It is thought that the effect | action which improves pigment dispersibility is adsorbed by the pigment | dye, or the aromatic site | part of the aromatic dicarboxylic acid imide anion which is a counter ion of a quaternary ammonium base adsorb | sucks with the pigment skeleton site | part of a pigment. That is, since the dispersing agent of this invention is a component which disperse | distributes a pigment favorably by this effect | action, it does not specifically limit about the kind of pigment to disperse.

In a pigment dispersion composition, it is preferable that it is 5 mass parts-200 mass parts with respect to 100 mass parts of pigments, It is more preferable that they are 10 mass parts-100 mass parts, It is more preferable that they are 10 mass parts-50 mass parts.

As a pigment, although any of an organic pigment and an inorganic pigment may be sufficient, the organic pigment which has an organic compound as a main component is especially preferable. As a pigment, pigments of each color, such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment, are mentioned, for example. The structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindolin pigments, quinacridone pigments And polycyclic pigments such as indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. There may be only one type of pigment contained in a pigment dispersion composition, and two or more types may be sufficient as it.

Specific examples of the pigment include CIPigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, Red pigments such as 146, 149, 168, 177, 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; CIPigment 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, 188, 193, 194, 213; Orange pigments such as C.I. Pigment Orange 36, 38, 43; Blue pigments such as C.I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and the like; Green pigments such as C.I. Pigment Green 7, 36, 58; Purple pigments, such as C.I. Pigment Violet 23, 32, 50, etc. are mentioned. Pigments include CIPigment Red 254, CIPigment Red 255, CIPigment Red 264, CIPigment Blue 15, CIPigment Blue 15: 2, CIPigment Blue 15: 3, CIPigment Blue 15: 4, CIPigment Blue 15 : 6, CIPigment Blue 16, CIPigment Green 7, CIPigment Green 36, CIPigment Green 58 and the like.

The upper limit of content of the pigment in a pigment dispersion composition is 80 mass% normally in solid content whole quantity of a pigment dispersion composition, It is preferable that it is 70 mass%, It is more preferable that it is 60 mass%. Moreover, the lower limit of content of the pigment in a pigment dispersion composition is 10 mass% normally in solid content whole quantity of a pigment dispersion composition, It is preferable that it is 20 mass%, It is more preferable that it is 30 mass%.

As a dispersion medium, a conventionally well-known organic solvent can be used, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol -t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxy Methylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene Glycol monoalkyl ethers such as glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether ; 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 Glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether; Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl iso amyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl Ketones such as ketone, methylnonyl ketone, and methoxymethylpentanone; 1, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxypropanol, methoxymethylpentanol, glycerin, benzyl alcohol, etc. Valent or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene and cumene; 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, Ethylbenzoate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, 3-methoxypropionic acid propyl, 3-Methoxylate Chain or cyclic esters such as butyl oxypropionate and γ-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles, such as acetonitrile and benzonitrile, etc. are mentioned. It is preferable that an organic solvent is glycol alkyl ether acetates, monohydric, or polyhydric alcohol from a viewpoint of dispersibility, such as a pigment, the solubility of a dispersing agent and the coating property of a pigment dispersion composition. There may be only one type of solvent contained in a pigment dispersion composition, and two or more types may be sufficient as it.

Content of the dispersion medium in a pigment dispersion composition is not specifically limited, It can adjust suitably. The upper limit of content of the dispersion medium in the pigment dispersion composition is usually 99% by mass. Moreover, the lower limit of content of the dispersion medium in a pigment dispersion composition is 70 mass% normally in consideration of the viscosity suitable for application | coating of a pigment dispersion composition, and it is preferable that it is 80 mass%. The dispersion medium may be used as a solvent for dissolving and removing the precipitate formed from the pigment dispersion composition.

It is preferable to further contain the acidic pigment derivative which has an acidic group in the pigment dispersion composition of this invention in order to make it adsorb by adsorbing the tertiary amino group and the quaternary ammonium base in the block copolymer which characterize this invention used for a dispersing agent. This dye derivative introduce | transduces the acidic functional group into the pigment | dye skeleton. As the dye skeleton, a skeleton identical or similar to the pigment constituting the pigment dispersion composition, and a skeleton identical or similar to the compound used as the raw material of the pigment is preferable. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, a perylene dye skeleton, and the like. As an acidic group introduce | transduced into a dye skeleton, a carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable. In addition, sulfonic acid groups are preferable from synthetic reasons and from acidity strength. Moreover, although an acidic group may couple | bond directly with a pigment | dye skeleton, Hydrocarbon groups, such as an alkyl group and an aryl group; You may bind to a pigment skeleton through ester, ether, sulfonamide, and urethane bonds.

Binder resin may be included in the pigment dispersion composition of this invention. The binder resin may be a polymer, for example. When the binder resin is a polymer, specific examples of the monomer constituting the polymer include, for example, carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid and maleic anhydride. ; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate (Meth) acrylic acid esters such as benzyl acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and cyclododecyl (meth) acrylate; Styrene, α-methylstyrene, 4-methylstyrene (p-methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxy Styrene), p-tert-butyl styrene, pn-butyl styrene, p-tert-butoxy styrene, etc. are mentioned.

When using a pigment dispersion composition as a coloring agent for color filters, it is preferable that binder resin is a copolymer of a carboxyl group-containing unsaturated monomer and (meth) acrylic acid ester. As a specific example of such a copolymer, the copolymer of (meth) acrylic acid and butyl (meth) acrylic acid, the copolymer of (meth) acrylic acid and benzyl (meth) acrylic acid, (meth) acrylic acid and butyl (meth) acrylate, and (meth) A copolymer of benzyl acrylate etc. are mentioned. From the viewpoint of affinity between the binder resin and the pigment, the binder resin is particularly preferably a copolymer of (meth) acrylic acid and benzyl (meth) acrylic acid. In the copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylic acid ester, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, preferably 10% by mass to 70% by mass, in all monomer components. It is more preferable that it is mass%-70 mass%. It is preferable that Mw is 3,000-100,000, It is more preferable that it is 5,000-50,000, It is more preferable that it is 5,000-20,000. If Mw of binder resin is 3,000 or more, heat resistance, film strength, etc. of the coating film formed from the pigment dispersion composition will become favorable, and if Mw is 100,000 or less, developability by the aqueous alkali solution of this coating film will become more favorable.

When using a pigment dispersion composition as a color filter coloring agent, it is preferable that the acid value of binder resin is 20 mgKOH / g-170 mgKOH / g, It is more preferable that it is 50 mgKOH / g-150 mgKOH / g, 90 mgKOH / g-150 mgKOH / g Is more preferred. If the acid value of binder resin is 20 mgKOH / g or more, the alkali developability at the time of making a pigment dispersion composition into a coating film will become more favorable, and if it is 170 mgKOH / g or less, heat resistance will become favorable.

There may be only one type of binder resin contained in a pigment dispersion composition, and two or more types may be sufficient as it. In a pigment dispersion composition, it is preferable that content of binder resin is 5 mass parts-200 mass parts with respect to 100 mass parts of pigments, It is more preferable that they are 10 mass parts-100 mass parts, It is more preferable that they are 10 mass parts-50 mass parts. .

A pigment dispersion composition is obtained by mixing a pigment, a dispersing agent, a dispersion medium, a pigment derivative, binder resin, etc. using mixed dispersers, such as a paint shaker, a bead mill, a ball mill, a dissolver, a kneader, for example. It is preferable to filter a pigment dispersion composition after mixing.

The pigment dispersion composition may contain other additives as needed. As another additive, a photopolymerizable monomer, a photoinitiator, a pH adjuster, antioxidant, a ultraviolet absorber, a light stabilizer, a preservative, a mold inhibitor, etc. are mentioned, for example. As a photopolymerizable monomer, the compound etc. which have at least two ethylenically unsaturated double bonds compatible with binder resin are preferable. As such a compound, when using a pigment dispersion composition as a color filter coloring agent, the compound which has alkali solubility, and has 1 or more acidic group and 2 or more ethylenically unsaturated bond in 1 molecule is preferable, and 1 or more in 1 molecule More preferred are compounds having an acidic group and at least three ethylenically unsaturated bonds. As a compound which has at least 2 ethylenically unsaturated double bond, polyfunctional (meth) acrylates, such as bifunctional (meth) acrylate and trifunctional or more (meth) acrylate, are mentioned. Among these, trifunctional or more than (meth) acrylate is preferable. As a compound which has 1 or more acidic group and 2 or more ethylenically unsaturated bond in 1 molecule, an acidic group containing polyfunctional (meth) acrylate is more preferable, and a trifunctional or more acidic group containing polyfunctional (meth) acrylate is Particularly preferred. What is necessary is just to be able to develop alkali as an acidic group, For example, a carboxy group, a sulfonic acid group, a phosphoric acid group etc. are mentioned. In view of further improving the alkali developability and handleability of the resin composition, the acidic group is preferably a carboxyl group.

The coating film of a pigment dispersion composition can be formed on a board | substrate by apply | coating a pigment dispersion composition on a board | substrate by methods, such as a spin coating method, a roll coating method, and a slit coating method. After apply | coating a pigment dispersion composition on a board | substrate, you may dry (desolvent process) etc. as needed.

When using the pigment dispersion composition of this invention as a patterning material of a color filter, etc., for example, since the block copolymer which characterizes this invention used for a dispersing agent is excellent in heat resistance, the contrast ratio before and behind a process with high temperature falls, It can be expected to suppress the color change and the like.

Example

Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these specific examples. In addition, various physical properties were measured with the following apparatus. In addition, the meaning of an abbreviation is as follows.

BTEE: ethyl-2-methyl-2-n-butylterranyl-propionate

DBDT: Dibutyl Di telluride

AIBN: 2,2'-azobis (isobutyronitrile)

MMA: Methyl methacrylate

BMA: Butyl methacrylate

EHMA: 2-ethylhexyl methacrylate

BzMA: benzyl methacrylate

M4EGM: methoxy polyethylene glycol monomethacrylate (brand name: BLEMMER PME-200, Nichi Corporation)

HEMA: 2-hydroxyethyl methacrylate

THFMA: tetrahydrofurfuryl methacrylate

PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (made by Daicel Kagaku Corporation, PLACCEL (registered trademark) FM5)

MAA: methacrylic acid

DMAEMA: dimethylaminoethyl methacrylate

BzCl: benzyl chloride

PIK: Potassium Phthalimide

NaSS: sodium p-styrene sulfonate

NaTS: sodium p-toluenesulfonic acid

NaBA: Sodium Benzoate

NaHPPA: monosodium phenylphosphonic acid

PMA: propylene glycol monomethyl ether acetate

MP: 1-methoxy-2-propanol

AcOEt: ethyl acetate

(Polymerization rate)

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

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))

It calculated | required by the gel permeation chromatography (GPC) using the high performance liquid chromatography (Tosoh make, model: HLC8320). The column uses SHODEX KF-603 (Φ6.0 mm x 150 mm) (manufactured by SHODEX) as a mobile phase with 30 mmol / L lithium bromide-30 mmol / L acetic acid-N-methylpyrrolidone and a differential refractive index detector as a detector. did. The measurement conditions were 40 degreeC of column temperature, 100 mg / mL of sample concentration, 10 microliters of sample injection amount, and 0.6 mL / min of flow velocity. A calibration curve (calibration curve) was created using polystyrene (TSK Standard, manufactured by Tosoh Corporation) as a standard substance, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. The molecular weight distribution (PDI) was computed from these measured values.

(Amine value)

An amine number is shown by the mass of a basic component and equivalent potassium hydroxide (KOH) per 1g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized and titrated with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: 915 KF Ti-touch, manufactured by Metrohm). The amine number (B) was computed by following Formula by making the inflection point of a titration pH curve into a titration end point.

B = 56.11 × Vs × 0.1 × f / w

B: amine number (mgKOH / g)

Vs: amount of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration (mL)

f: Titer of 0.1 mol / L hydrochloric acid / 2-propanol solution

w: Mass (g) (solid content conversion) of the measurement sample

(Acid value)

The 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, and the obtained solution was neutralized titrated with a 0.5 mol / L potassium hydroxide / ethanol solution. The acid value (A) was calculated by the following equation.

A = 56.11 × Vs × 0.5 × f / w

A: acid value (mgKOH / g)

Vs: The amount of 0.5 mol / L potassium hydroxide / ethanol solution required for titration (mL)

f: titer of 0.5 mol / L potassium hydroxide / ethanol solution

w: Mass (g) (solid content conversion) of the measurement sample

(Viscosity)

The viscosity was measured at rotor rotation speed of 100 rpm at 25 degreeC using the E-type viscosity meter (brand name: TVE-22L, the earthenware company make) using the rotor (1 degrees 34 '* R24).

(Heating weight reduction temperature)

It measured using the thermogravimetry and differential thermal simultaneous measurement apparatus (TG-DTA) (TG-DTA6300 by SII Nanotechnology). The measurement sample was dried under reduced pressure at the temperature of 130 degreeC for 2 hours before a measurement. Measurement conditions were made into about 10 mg of sample mass, 200 ml / min of air inflow rate, 10 degreeC / min of temperature increase rate, and 40 degreeC-600 degreeC of measurement temperature range. 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 reduction temperature.

(Content of halogen anion)

Sample adjustment was performed as follows. About 10 mg of mass of a 2nd composition was thrown into the combustion furnace (brand name: AQF-2100H, the Mitsubishi Kagaku Analyte). As for the heater of a combustion furnace, argon 200 mL / min, oxygen 400 mL / min, humidification argon 100 mL / min, and combustion furnace stay time were 900 minutes (inside), gas flow rate. The exhaust gas was captured by a collector (trade name: AU-250, manufactured by Mitsubishi Kagaku Analtech). Ultrapure water was used as the absorbent liquid, and 35 mL of the obtained absorbent liquid was diluted to 50 mL using ultrapure water to adjust the sample solution.

Content of the halogen anion was measured using ion chromatography (brand name: DIONEX ICS-1600, manufactured by Thermo Scientific). The column used Ion Pac AS-14A (made by DIONEX), and the eluent used for the anion analysis eluent (brand name: AS12A, made by DIONEX). The measurement conditions were 25 µL of sample injection amount and 1.5 mL / min of flow rate. The calibration curve (calibration curve) was created using the standard liquid of 1 ppm and 2 ppm of chlorine anion concentration as a standard substance, and the chlorine anion concentration was computed.

<Production of Copolymer>

(Precursor No. 1 of the block copolymer)

MMA 46.1g, BMA 22.2g, EHMA 20.9g, BzMA 15.4g, M4EGM 8.1g, MAA 8.1g, AIBN 0.82g, PMA 80.5g were placed in a flask equipped with an argon gas introduction tube and a stirrer. 7.49g and 4.61g of DBDT were added, and it reacted at 60 degreeC for 15 hours, and polymerized A block. The polymerization rate was 99%.

A mixed solution of 54.3 g of DMAEMA, AIBN 0.41 g, and PMA 36.2 g previously substituted with argon was added to the reaction solution, and the mixture was reacted at 60 ° C for 10 hours to polymerize the B block. The polymerization rate was 98%.

After completion | finish of reaction, methanol (165g) substituted by argon was previously added and diluted to the reaction liquid, and benzyl chloride (15.3g) was added to the diluted solution, and it quaternized by making it react at 60 degreeC for 10 hours.

After completion of the reaction, the mixture was poured into stirring n-heptane. The precipitated polymer was suction filtered and dried to obtain precursor No. 1 of the block copolymer. Precursor No. 1 of the obtained block copolymer had a Mw of 7618, a PDI of 1.30, an acid value of 32 mgKOH / g, an amine value of 64 mgKOH / g, and a heating weight reduction temperature of 254 ° C.

(Precursor Nos. 2 to 12 of the block copolymer)

Precursor Nos. 2 to 12 of the block copolymer were prepared in the same manner as in the preparation method of the precursor No. 1 of the block copolymer. In Table 1, 2, the used raw material monomer, the organic tellurium compound, the organic de tellurium compound, the azo polymerization initiator, the solvent, the quaternizing agent, the reaction conditions, and the polymerization rate were shown. In Tables 3 and 4, the composition, Mw, PDI, acid value, amine value, and heating weight reduction temperature of the precursors of the respective block copolymers are shown.

(First Composition No. 31 of Block Copolymer)

PMA 110g and MP110g were added and dissolved in 87.5g of precursor No. 1 of the block copolymer obtained above. PIK 11.2g was added to the obtained solution, and it was made to react anion by making it react at 60 degreeC for 20 hours. After filtering the reaction solution, the solvent was removed from the filtrate to obtain the first composition No. 31 of the block copolymer. Obtained 1st composition No. 31 has Mw of 7479 and PDI of 1.23 of the block copolymer contained, the acid value of 31 mgKOH / g, the amine value of 101 mgKOH / g, and the weight loss temperature of 273 degreeC of 1st composition No.31 are 273 degreeC. It was.

(1st composition No. 32-46 of a block copolymer)

1st composition No. 32-46 was produced like the manufacturing method of 1st composition No. 31 of a block copolymer. In Tables 5 and 6, the used raw material copolymer, an anion exchanger, a solvent, and reaction conditions were shown. In Tables 7, 8, the composition of the block copolymer contained in the first composition, the acid value of the Mw, PDI, and the first composition, the amine value, and the heating weight reduction temperature were shown.

(2nd composition No. 51 of a block copolymer)

PMA 110g and MP110g were added and dissolved in 87.5g of precursor No. 1 of the block copolymer obtained above. PIK 11.2g was added to the obtained solution, and it was made to react anion by making it react at 60 degreeC for 20 hours. After cooling the obtained reaction liquid, ethyl acetate and water were added, and it stirred at 40 degreeC for 1 hour. Separation was performed to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure and dried to obtain a second composition No. 51 of the block copolymer. As for 2nd composition No. 51 of the obtained block copolymer, Mw of the block copolymer contained was 7852 and PDI was 1.21. Moreover, the acid value of the 2nd composition was 32 mgKOH / g, the amine value was 89 mgKOH / g, the heating weight loss temperature was 291 degreeC, and chlorine anion content was 3501 ppm (solid content conversion).

(2nd composition No. 52-65 of a block copolymer)

2nd composition No.53-65 was produced similarly to the manufacturing method of 2nd composition No.51 of a block copolymer. In Tables 9 and 10, the composition of the block copolymer contained in the second composition, the acid value of the Mw, PDI and the second composition, the amine value, and the heating weight reduction temperature were shown. The chlorine anion content of obtained 2nd composition No. 59 was 6615 ppm (solid content conversion).

<Production of Pigment Dispersion Composition>

(Pigment Dispersion Composition 1)

10 mass parts of CIPigment Red 254 (brand name: BKCF, Chiba Specialty Chemicals company), 3 mass parts of precursor No. 1 of a block copolymer, mass ratio of binder resin (benzyl methacrylate / methacrylic acid = 80/20) The mixture was prepared so that 3 mass parts, 3 mass parts of MP, and 81 mass parts of PMA of thing superposed | polymerized with the polymer, Mw = 12024, PDI = 1.83, acid value 130 mgKOH / g, solid content 39 mass%, and planetary ball mill (0.3 mm) A pigment dispersion composition was prepared by stirring with zirconia beads for 2 hours. The viscosity of the obtained pigment dispersion composition was 4.0 mPa · s.

(Pigment Dispersion Composition 2)

10 mass parts of CIPigment Red 254 (brand name: BKCF, Chiba Specialty Chemicals company), 3 mass parts of 2nd composition No.51 of a block copolymer, binder resin (benzyl methacrylate / methacrylic acid = 80/20) The formulation was prepared so that 3 mass parts, MP 3 mass parts, and PMA 81 mass parts of the thing superposed | polymerized by the mass ratio of Mw = 12024, PDI = 1.83, acid value 130 mgKOH / g, solid content 39 mass%), and a planetary ball mill ( A pigment dispersion composition was prepared by stirring with 0.3 mm zirconia beads) for 2 hours. The viscosity of the obtained pigment dispersion composition was 3.0 mPa · s.

The following embodiments are included in the present invention.

(Embodiment 1)

It has an A block containing the structural unit derived from the vinyl monomer which has an acidic group, and the B block containing the structural unit represented by following General formula (1), and the structural unit represented by following General formula (2), It is characterized by the above-mentioned. Block copolymer.

[In Formula (1), R <^11> , R <^12> and R <^13> respectively independently represents the 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. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents at least one member selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions.]

[In formula (2), R <^21> and R <^22> represents the linear or cyclic hydrocarbon group which may respectively have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

(Embodiment 2)

The block copolymer according to Embodiment 1 which is an A-B type block copolymer.

(Embodiment 3)

The block copolymer as described in Embodiment 1 or 2 whose content rate of the structural unit derived from the vinyl monomer which has the said acidic group is 2 mass%-20 mass% in 100 mass% of said A blocks.

(Embodiment 4)

The block copolymer as described in any one of Embodiments 1-3 whose content rate of the structural unit represented by the said General formula (1) is 30 mass%-85 mass% in 100 mass% of said B blocks.

 (Embodiment 5)

The block copolymer as described in any one of Embodiments 1-4 whose content rate of the said A block is 35 mass%-85 mass% in 100 mass% of block copolymers.

Embodiment 6

The 1st composition containing the block copolymer as described in any one of embodiment 1-5.

(Embodiment 7)

The 1st composition as described in Embodiment 6 whose molecular weight distribution (PDI) of the said block copolymer is 2.0 or less.

Embodiment 8

The second composition obtained by washing with water and drying the first composition of Embodiment 7.

(Embodiment 9)

The dispersing agent containing the block copolymer as described in any one of Embodiments 1-6, the 1st composition as described in Embodiment 7, or the 2nd composition as described in Embodiment 8.

Embodiment 10

Pigment dispersion composition containing the dispersing agent as described in Embodiment 9, a pigment, and a dispersion medium.

(Embodiment 11)

The pigment dispersion composition as described in Embodiment 10 which is for color filters.

(Twelfth Embodiment)

Block copolymer which has the A block containing the structural unit derived from the vinyl monomer which has an acidic group, and the B block containing the structural unit represented by the following general formula (2), and the structural unit represented by the following general formula (3) (A) preparing a precursor of

At least one alkali metal salt selected from the group consisting of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid is applied to the precursor of the block copolymer obtained in the step (A) to obtain a block copolymer. Process (B) is provided, The manufacturing method of the block copolymer characterized by the above-mentioned.

[In formula (2), R <^21> and R <^22> represents the linear or cyclic hydrocarbon group which may respectively have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

[In formula (3), R <^31> , R <^32> and R <^33> respectively independently represents the linear or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ^- represents a halogen anion.]

(Embodiment 13)

The manufacturing method of the block copolymer as described in Embodiment 12 which prepares the precursor of the said 1st block copolymer in the said process (A) using living radical polymerization.

(Embodiment 14)

The manufacturing method of the block copolymer as described in Embodiment 12 or 13 provided with the process (C) of washing the block copolymer obtained at the said process (B).

Industrial availability

In the block copolymer of the present invention, alkali development is facilitated when the A block has an acidic group. Moreover, since the counter ion of the quaternary ammonium cation of B block is aromatic dicarboxylic acid imide anion, aromatic sulfonic acid anion, aromatic phosphonic acid anion, or aromatic carboxylic acid anion, it is excellent in heat resistance. Therefore, the block copolymer of this invention can be used suitably for the pigment dispersion composition for color filters used for manufacture of the color filter which employ | adopted alkali image development.

Claims (14)

It has an A block containing the structural unit derived from the vinyl monomer which has an acidic group, and the B block containing the structural unit represented by the following general formula (1), and the structural unit represented by the following general formula (2), Block copolymer.

[In Formula (1), R <^11> , R <^12> and R <^13> respectively independently represents the 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. X ¹ represents a divalent linking group. R ¹⁴ represents a hydrogen atom or a methyl group. Y ⁻ represents at least one member selected from the group consisting of aromatic dicarboxylic acid imide anions, aromatic sulfonic acid anions, aromatic phosphonic acid anions and aromatic carboxylic acid anions.]

[In formula (2), R <^21> and R <^22> respectively independently represents the chain | strand or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.] The method according to claim 1,
A block copolymer, which is an AB type block copolymer. The method according to claim 1,
The block copolymer whose content rate of the structural unit derived from the vinyl monomer which has the said acidic group is 2 mass%-20 mass% in 100 mass% of said A blocks. The method according to claim 1,
The block copolymer whose content rate of the structural unit represented by the said General formula (1) is 30 mass%-85 mass% in 100 mass% of said B blocks. The method according to claim 1,
The block copolymer whose content rate of the said A block is 35 mass%-85 mass% in 100 mass% of block copolymers. 1st composition containing the block copolymer of Claim 1. The method according to claim 6,
The 1st composition whose molecular weight distribution (PDI) of the said block copolymer is 2.0 or less. The 2nd composition obtained by washing with water and drying the 1st composition of Claim 7. The dispersing agent containing the block copolymer as described in any one of Claims 1-5, the 1st composition of Claim 6 or 7, or the 2nd composition of Claim 8. The pigment dispersion composition containing the dispersing agent of Claim 9, a pigment, and a dispersion medium. The method according to claim 10,
Pigment dispersion composition for color filters. Block copolymer which has the A block containing the structural unit derived from the vinyl monomer which has an acidic group, and the B block containing the structural unit represented by the following general formula (2), and the structural unit represented by the following general formula (3) (A) preparing a precursor of
At least one alkali metal salt selected from the group consisting of aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid is applied to the precursor of the block copolymer obtained in the step (A) to obtain a block copolymer. Process (B) is provided, The manufacturing method of the block copolymer characterized by the above-mentioned.

[In formula (2), R <^21> and R <^22> respectively independently represents the chain | strand or cyclic hydrocarbon group which may have a substituent. R ²¹ and R ²² may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²³ represents a hydrogen atom or a methyl group.]

[In formula (3), R <^31> , R <^32> and R <^33> respectively independently represents the linear or cyclic hydrocarbon group which may have a substituent. Two or more of R ³¹ , R ³² and R ³³ may be bonded to each other to form a cyclic structure. X ³ represents a divalent linking group. R ³⁴ represents a hydrogen atom or a methyl group. X ^- represents a halogen anion.] The method according to claim 12,
The manufacturing method of the block copolymer in the said process (A) which prepares the precursor of the said block copolymer using living radical polymerization. The method according to claim 12 or 13,
The manufacturing method of the block copolymer provided with the process (C) of washing the block copolymer obtained at the said process (B).